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United States Patent |
5,173,540
|
Saito
,   et al.
|
December 22, 1992
|
Catalyst component for producing highly crystalline olefin polymers and
a process for producing the same
Abstract
A catalyst component for producing highly crystalline olefin polymers
without causing any operational problems and stably and affording
therefrom a film having very few occurrence of voids and a superior
transparency, and a process for producing the catalyst component, which
catalyst component comprises a linear olefin-non-olefin block copolymer
having at least one linear olefin block copolymer and at leaast one
non-linear olefin polymer block and (a) a titanium trichloride composition
or (b) titanium, magnesium, a halogen and an electron donor as components
for a carrier, the content of the linear olefin polymer block being 0.1 to
49.5% by weight, the content of the non-linear olefin polymer block being
0.01 to 49.5% by weight, the ratio by weight of the linear olefin polymer
block to the non-linear olefin polymer block being 2/98 to 98/2 and in the
case of (a), the content of the titanium trichloride composition being
99.89 to 1.0% by weight.
Inventors:
|
Saito; Jun (Chibaken, JP);
Sanpei; Akihiko (Chibaken, JP)
|
Assignee:
|
Chisso Corporation (Osaka, JP)
|
Appl. No.:
|
509768 |
Filed:
|
April 17, 1990 |
Foreign Application Priority Data
| Apr 25, 1989[JP] | 1-105080 |
| May 16, 1989[JP] | 1-121950 |
Current U.S. Class: |
525/247; 525/268; 525/270; 525/288; 525/297; 525/319; 525/323 |
Intern'l Class: |
C08F 297/08 |
Field of Search: |
525/247,941,288,297,323
|
References Cited
U.S. Patent Documents
4210729 | Jul., 1980 | Hermans et al. | 525/247.
|
4210735 | Jul., 1990 | Hermans et al. | 526/119.
|
4582878 | Apr., 1986 | Chiba et al. | 525/68.
|
4603174 | Jul., 1986 | Okada et al. | 526/274.
|
4748207 | May., 1988 | Kakugo et al. | 525/297.
|
5061755 | Oct., 1991 | Suga et al. | 525/247.
|
Foreign Patent Documents |
62-275111 | Nov., 1987 | JP.
| |
2114581 | Aug., 1983 | GB.
| |
Primary Examiner: Seccuro, Jr.; Carman J.
Attorney, Agent or Firm: Philpitt; Fred
Claims
What we claim is:
1. A process for producing a titanium trichloride composition for producing
olefin polymers, which process comprises reacting TiCl.sub.4 with an
organoaluminum compound or a reaction product (I) of an organoaluminum
compound wi&h an electron donor (B.sub.1) to form a solid product (II),
subjecting said solid product (II) to a multi-stage polymerization
treatment once or more with each of 1 a linear olefin and 2 a non-linear
olefin to form a linear olefin-non-linear olefin block copolymer, and
further reacting said block copolymer with an electron donor (B.sub.2) and
an electron acceptor to form a solid product (III), the content of said
linear olefin polymer block in said (III) being made 10.0 to 49.3% by
weight and that of said non-linear olefin polymer block therein being made
1.5 to 47.6% by weight and the ratio by weight of said linear olefin
polymer block to said non-linear olefin polymer block being 2/98 to 98/2.
2. A production process according to claim 1 wherein said organoaluminum
compound is the one expressed by the formula
AlR.sup.8.sub.p R.sup.9.sub.p' X.sub.3-(p+p')
wherein R.sup.8 and R.sup.9 each represent a hydrocarbon radical selected
from alkyl group, cycloalkyl group or aryl group or an alkoxy group, X
represents a halogen atom and p and p' each represent an optional number
satisfying an expression of
0<p+p'.ltoreq.3.
3. A production process according to claim 1 wherein said non-linear olefin
is a branched olefin expressed by the formula
##STR13##
wherein R.sup.2 represents a linear hydrocarbon radical of 1 to 3 carbon
atoms which may contain silicon or silicon, and R.sup.3, R.sup.4 and
R.sup.5 each represent a linear hydrocarbon radical of 1 to 6 carbon atoms
which may contain silicon and any one of R.sup.3, R.sup.4 and R.sup.5 may
be hydrogen atom.
4. A production process according to claim 1 wherein said non-linear olefin
is a saturated ring-containing hydrocarbon monomer of 3 to 18 carbon atoms
expressed by the formula of CH.sub.2 .dbd.CH--R.sup.1 and R.sup.1 is
selected from the group consisting of
(a) saturated ring-containing hydrocarbon monomers,
(b) saturated ring-containing hydrocarbon monomers having silicon atoms in
the saturated ring structure, and
(c) saturated ring-containing hydrocarbon monomers having silicon atoms
outside the saturated ring structure.
5. A production process according to claim 1 wherein said non-linear olefin
is an aromatic monomer expressed by the formula
##STR14##
wherein n represents 0 or 1, m represents 1 or 2, R.sup.6 represents a
linear hydrocarbon radical of 1 to 6 carbon atoms which may contain
silicon, R.sup.7 represents a hydrogen atom, a halogen atom or a
hydrocarbon radical of 1 to 12 carbon atoms which may contain silicon, and
when m is 2 the R.sup.7 s may be the same or different.
6. The titanium trichloride composition produced by the process of claim 1.
7. The titanium trichloride composition produced by the process of claim 2.
8. The titanium trichloride composition produced by the process of claim 4.
9. The titanium trichloride composition produced by the process of claim 3.
10. The titanium trichloride composition produced by the process of claim
5.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a catalyst component used for producing highly
crystalline olefin polymers and a process for producing the same. More
particularly it relates to a catalyst component for producing highly
crystalline olefin polymers from which a film having a superior
transparency and very few voids is afforded, and a process for producing
the same.
2. Description of the Related Art
It has been well known that crystalline olefin polymers such as crystalline
polypropylene, etc. are obtained by polymerizing olefins by means of the
so-called Ziegler-Natta catalyst comprising a compound of a transition
metal of Groups IV to VI of the Periodic Table and an organometal compound
of a metal of Groups I to III of the Table. As the transition metal
compound catalyst component, various titanium trichloride compositions
have been particularly broadly used.
Among these titanium trichloride compositions, those of a type obtained by
reducing TiCl.sub.4 with an organoaluminum compound, followed by heat
treatment, afford a polymer having a good form; thus many improved
processes for producing the above type compositions have been researched.
For example, a process of reducing TiCl.sub.4 with an organoaluminum
compound, followed by treating the resulting titanium trichloride with an
electron donor and TiCl.sub.4 to thereby enhance the catalyst activity and
reduce the quantity of amorphous polymers formed (Japanese patent
publication No. Sho 53-3,356/1978) and the like processes have been
disclosed.
The present inventors have already proposed a number of processes in this
field. According to the following processes among the above, the storage
stability of titanium trichloride compositions, the polymerization
activity, the crystallinity of the resulting olefin polymers, etc. have
been notably improved as compared with those of conventional processes:
A process of producing olefin polymers using a titanium trichloride
composition obtained by-reacting TiCl.sub.4 with a reaction product of an
organoaluminum compound with an electron donor, followed by reacting the
resulting solids with an electron donor and an electron acceptor (Japanese
patent publication No. Sho 59-28,573/1984), and
A process of producing olefin polymers using a titanium trichloride
composition obtained by reacting TiCl.sub.4 with a reaction product of an
organoaluminum compound with an electron donor, followed by subjecting the
resulting solids to polymerization treatment with an olefin and reacting
the resulting material with an electron donor and an electron acceptor
(Japanese patent application laid-open No. Sho 58-17,104/1983).
Further, on the other hand, in recent years, there has been energetically
researched a process for producing olefin polymers which comprises using a
titanium-containing solid catalyst component containing Ti, Mg, a halogen
and an electron donor, which component exhibits a very high polymerization
activity while retaining a high stereo-regularity, and polymerizing
olefins in the presence of a catalyst obtained by combining the above
solid catalyst component, an organoaluminum compound and an electron donor
together (e.g. Japanese patent application laid-open No. Sho
58-83,006/1983, etc.).
The present inventors have also already proposed a number of processes. For
example, we have disclosed processes for producing olefin polymers having
a high stereoregularity and a good particle form with a high
polymerization activity (e.g. Japanese patent application laid-open Nos.
Sho 61-209,207/1986, Sho 62-104,810/1987, Sho 62-104,811/1987, Sho
62-104,812/1987, Sho 62-104,813/1987, etc.).
However, while these improved processes are provided with the
above-mentioned advantages, films prepared from the resulting polyolefins
are translucent so that the commodity value is often damaged depending on
the fields of use applications; thus improvement in the transparency has
been desired.
On the other hand, improvement in the transparency of films prepared from
olefin polymers has been attempted. For example, processes of adding a
nucleating agent such as aluminum salts of aromatic carboxylic acids
(Japanese patent publication No. Sho 40-1,652/1965), benzylidene sorbitol
derivatives (Japanese patent application laid-open No. Sho
51-22,740/1976), etc. to polypropylene have been proposed. However, when
aluminum salts of aromatic carboxylic acids are used, their dispersibility
in the resulting polymer is not only inferior, but also the effectiveness
of improvement in the transparency of the resulting film is insufficient,
while when benzylidene sorbitol derivatives are used, a definite
improvement in the transparency is observed, but there have been raised
problems that their smell at the time of processing is strong, a bleeding
phenomenon(exudation) occurs, etc.
For solving the above-mentioned problem at the time of addition of
nucleating agents, there have been proposed processes of polymerizing
propylene using a catalyst obtained by polymerizing a small quantity of
vinylcyclohexane, p-t-butylstyrene, allyltrimethylsilane,
4,4-dimethylpentene-1, etc., followed by preactivation treatment (Japanese
patent application laid-open Nos. Sho 60-139,710/1985, Sho
63-15,803/1988, Sho 63-15,804/1988, Sho 63-218,709/1988, etc.). The
present inventors produced polypropylene according to the proposed
processes, and as a result found that in any of the processes, the
polymerization activity of propylene not only lowered, but also there
occurred operational problems such as formation of bulk polymer, scale
adhesion onto the wall of polymerization vessel, inferior controllability
of polymerization reaction, etc. Thus these processes could not be
employed in the case of commercial, long term, continuous polymerization,
particularly in the case of gas phase polymerization process wherein
olefin polymerization was carried out.
Further, when the resulting polypropylene was processed into film, a
definite improvement in the transparency was observed, but a large number
of voids occurred in the film to thereby damage the commodity value.
Further, as a similar technique, there has been proposed a process of
polymerizing propylene using a transition metal catalyst component having
vinylcyclohexane polymer, allyltrimethylsilane polymer, etc. added in
advance midway during the preparation of the component (Japanese patent
application laid-open No. Sho 63-69,809/1988). However, since the proposed
process requires a separate step of preparing the vinylcyclohexane
polymer, allyltrimethylsilane polymer, etc., commercial disadvantage is
not only brought about, but also there has been raised the above-mentioned
problem that voids occur in the resulting film as observed in the prior
art.
The present inventors have made extensive research on a transition metal
catalyst component for producing olefin polymers, having overcome the
above-mentioned problems of the prior art, that is, capable of producing
crystalline olefin polymers stably and for a long term, and when made into
film, affording a film having few voids and an improved transparency. As a
result, we have found a titanium trichloride composition or a supported
type titanium catalyst component, each having a linear olefin-non-linear
olefin block compolymer contained therein according to a specified
process, and further have found that when an olefin polymer is produced
using a catalyst having at least an organoaluminum compound combined with
the above titanium trichloride composition or the supported type titanium
catalyst component, the above-mentioned problems of the prior art in the
aspect of production and quality can be solved.
SUMMARY OF THE INVENTION
As apparent from the foregoing, the object of the present invention is to
provide a titanium trichloride composition as a catalyst component or a
supported type catalyst component for producing highly crystalline olefin
polymers without causing any operational problems and stably, and
affording therefrom a film having very few occurrence of voids and
superior transparency and a process for producing the catalyst component.
The present invention has the following constitutions:
(1) A titanium trichloride composition for producing olefin polymers, which
composition comprises a linear olefin-non-linear olefin block copolymer
having at least one linear olefin polymer block and at least one nonlinear
olefin polymer block, and a titanium trichloride composition, the content
of said linear olefin polymer block being 0.1 to 49.5% by weight, the
content of said non-linear olefin polymer block being 0.01 to 49.5% by
weight, the ratio by weight of said linear olefin polymer block to said
non-linear olefin polymer block being 2/98 to 98/2 and the content of said
titanium trichloride composition being 99.89 to 1.0% by weight.
(2) A titanium trichloride composition according to item (1) wherein said
non-linear olefin polymer block is a saturated ring-containing hydrocarbon
polymer block consisting of repetition units expressed by the formula
##STR1##
wherein R.sup.1 represents a saturated ring-containing hydrocarbon radical
of 3 to 18 carbon atoms which has a saturated ring structure of a
hydrocarbon which may contain silicon.
(3) A titanium trichloride composition according to item (1) wherein said
non-linear olefin polymer block is a branched olefin polymer block
consisting of repetition units expressed by the formula
##STR2##
wherein R.sup.2 represents a linear hydrocarbon radical of 1 to 3 carbon
atoms which may contain silicon or silicon and R.sup.3, R.sup.4 and
R.sup.5 each represent a linear hydrocarbon radical of 1 to 6 carbon atoms
which may contain silicon, but any one of R.sup.3, R.sup.4 and R.sup.5 may
be hydrogen atom.
(4) A titanium trichloride composition according to item (1) wherein said
non-linear olefin polymer block is an aromatic polymer block consisting of
repetition units expressed by the formula
##STR3##
wherein n represents 0 or 1, m represents 1 or 2, R.sup.6 represents a
linear hydrocarbon radical of 1 to 6 carbon atoms which may contain
silicon, R.sup.7 represents a hydrocarbon radical of 1 to 12 carbon atoms
which may contain silicon, hydrogen atom or a halogen atom and when m
represents 2, the respective R.sup.7 s may be same or different.
(5) A process for producing a titanium trichloride composition for
producing olefin polymers, which process comprises reacting TiCl.sub.4
with an organoaluminum compound or a reaction product (I) of an
organoaluminum compound with an electron donor (B.sub.1) to form a solid
product (II), subjecting said solid product (II) to a multi-stage
polymerization treatment once or more with each of 1 a linear olefin and 2
a non-linear olefin to form a linear olefin-non-linear olefin block
copolymer, and further reacting said block copolymer with an electron
donor (B.sub.2) and an electron acceptor to form a solid product (III),
the content of said linear olefin polymer block in said (III) being made
0.1 to 49.5% by weight and that of said non-linear olefin polymer block
therein being made 0.01 to 49.5% by weight and the ratio by weight of said
linear olefin polymer block to said non-linear olefin polymer block being
2/98 to 98/2.
(6) A production process according to item (5) wherein said organoaluminum
compound is the one expressed by the formula
AlR.sup.8.sub.p R.sup.9.sub.p' X.sub.3-(p+p')
wherein R.sup.8 and R.sup.9 each represent a hydrocarbon radical such as
alkyl group cycloalkyl group, aryl group, etc. or an alkoxy group, X
represents a halogen atom and p and p' each represent an optional number
satisfying an expression of
0<p+p'.ltoreq.3.
(7) A production process according to item (5) wherein said non-linear
olefin is a saturated ring-containing hydrocarbon monomer expressed by the
formula of CH.sub.2 =CH--R.sup.1 wherein R.sup.1 represents a saturated
ring-containing hydrocarbon of 3 to 18 carbon atoms which has a saturated
ring structure of a hydrocarbon which may contain silicon.
(8) A production process according to item (5) wherein said non-linear
olefin is a branched olefin expressed by the formula
##STR4##
wherein R.sup.2 represents a linear hydrocarbon radical of 1 to 3 carbon
atoms which may contain silicon or silicon, and R.sup.3, R.sup.4 and
R.sup.5 each represent a linear hydrocarbon radical of 1 to 6 carbon atoms
which may contain silicon and any one of R.sup.3, R.sup.4 and R.sup.5 may
be hydrogen atom.
(9) A production process according to item (5) wherein said non-linear
olefin is an aromatic monomer expressed by the formula
##STR5##
wherein n represents 0 or 1, m represents 1 or 2, R.sup.6 represents a
linear hydrocarbon radical of 1 to 6 carbon atoms which may contain
silicon, R.sup.7 represents a hydrocarbon radical of 1 to 12 carbon atoms
which may contain silicon, hydrogen atom or a halogen atom, and when m
represents 2, the respective R.sup.7 s may be same or different.
(10) A supported type titanium catalyst component comprising a linear
olefin-non-linear olefin block copolymer having at least one linear olefin
polymer block and at least one non-linear olefin polymer block and
titanium, magnesium, a halogen and an electron donor as indispensable
components, the content of said linear olefin polymer block in said block
copolymer being 0.1 to 49.5% by weight, the content of said non-linear
olefin block copolymer therein being 0.01 to 49.5% by weight and the ratio
by weight of said linear olefin polymer block to said nonlinear olefin
polymer block being 2/98 to 98/2.
(11) A supported type titanium catalyst component according to item (10),
wherein said non-linear olefin polymer block is a saturated
ring-containing hydrocarbon polymer block consisting of repetition units
expressed by the formula
##STR6##
wherein in R.sup.1 represents a saturated ring-containing hydrocarbon
radical of 3 to 18 carbon atoms which has a saturated ring structure which
may contain silicon.
(12) A supported type titanium catalyst component according to item (10),
wherein said non-linear olefin polymer block is a branched olefin polymer
block consisting of repetition units expressed by the formula
##STR7##
wherein R.sup.2 represents a linear hydrocarbon radical of 1 to 3 carbon
atoms which may contain silicon or silicon, R.sup.3, R.sup.4 and R.sup.5
each represent a linear hydrocarbon radical of 1 to 6 carbon atoms which
may contain silicon and any one of R.sup.3, R.sup.4 and R.sup.5 may be
hydrogen atom.
(13) A supported type titanium catalyst component according to item (10),
wherein said non-linear olefin polymer block is an aromatic polymer block
consisting of repetition units expressed by the formula
##STR8##
wherein n represents 0 or 1, m represents 1 or 2, R.sup.6 represents a
linear hydrocarbon radical of 1 to 6 carbon atoms which may contain
silicon, R.sup.7 represents a hydrocarbon radical of 1 to 12 carbon atoms
which may contain silicon, hydrogen atom or a halogen atom and when m
represents 2, the respective R.sup.7 s may be same or different.
(14) A process for producing a supported type titanium catalyst component
for producing olefin polymers, which process comprises subjecting a solid
product (I) obtained by contacting a liquefied magnesium compound with a
depositing agent, a halogen compound, an electron donor and a titanium
compound (T.sub.1) to a multi-stage polymerization treatment once or more
each with 1 a linear olefin and 2 a non-linear olefin in the presence of
an organoaluminum compound to form a linear olefin-non-linear olefin block
copolymer as a solid product (II) and reacting a halogenated titanium
compound (T.sub.2) with said solid product (II), the content of said
olefin polymer block in said supported type titanium catalyst component
being made 0.1 to 49.5% by weight, that of said non-olefin polymer block
therein being made 0.01 to 49.5% by weight and the ratio by weight of said
linear olefin polymer block to said non-linear olefin polymer block being
2/98 to 98/2.
(15) A production process according to item (14), wherein said
organoaluminum compound is an organoaluminum compound expressed by the
formula
AlR.sup.8.sub.l R.sup.9.sub.l' X.sub.3-(l+l')
wherein R.sup.8 and R.sup.9 each represent a hydrocarbon radical selected
from the group consisting of an alkyl group, a cycloalkyl group and an
aryl group or an alkoxy group, X represents a halogen atom and l and l'
each represent an optional number satisfying an expression of
0<l+l'.ltoreq.3.
(16) A production process according to item (14), wherein said non-linear
olefin is a saturated ring-containing hydrocarbon monomer expressed by the
formula
CH.sub.2 .dbd.CH--R.sup.1
wherein R.sup.1 represents a saturated ring-containing hydrocarbon radical
of 3 to 18 carbon atoms which has a saturated ring structure of a
hydrocarbon which may contain silicon.
(17) A production process according to item (14), wherein said non-linear
olefin is a branched olefin expressed by the formula
##STR9##
wherein R.sup.2 represents a linear hydrocarbon radical of 1 to 3 carbon
atoms which may contain silicon or silicon, R.sup.3, R.sup.4 and R.sup.5
each represent a linear hydrocarbon radical of 1 to 6 carbon atoms which
may contain silicon and any one of R.sup.3, R.sup.4 and R.sup.5 may be
hydrogen atom.
(18) A production process according to item (14), wherein said non-linear
olefin is an aromatic monomer expressed by the formula
##STR10##
wherein n represents 0 or 1, m represents 1 or 2, R.sup.6 represents a
linear hydrocarbon radical of 1 to 6 carbon atoms which may contain
silicon, R.sup.7 represents a hydrocarbon radical of 1 to 12 carbon atoms
which may contain silicon, hydrogen atom or a halogen atom and when m
represents 2, the respective R.sup.7 s may be same or different.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 each show a chart of production steps (flowsheet) of the
catalyst component, for illustrating the process of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The constitutions of the present invention described in the above items (1)
to (9) will be described in more detail.
As described above, the titanium trichloride composition for producing
olefin polymers, of the present invention is a titanium trichloride
composition comprising a linear olefin-non-linear olefin block copolymer
(hereinafter often abbreviated to a specified block copolymer) having at
least one linear olefin polymer block and at least one non-linear olefin
polymer block, and the production process of the composition will be
described below.
The production of the titanium trichloride composition is carried out as
follows:
An organoaluminum compound is at first reacted with an electron donor
(B.sub.1) to obtain a reaction product (I), which is then reacted with
TiCl.sub.4 or with an organoaluminum compound and TiCl.sub.4 to obtain a
solid product (II), which is then subjected to a multi-stage
polymerization treatment once or more with each of 1 an linear olefin and
2 a non-linear olefin to form a linear olefin-non-linear olefin block
copolymer, which is further reacted with an electron donor (B.sub.2) and
an electron acceptor to obtain a final solid product (III) which is the
titanium trichloride composition of the present invention.
In addition, the terms "polymerization treatment" referred to herein means
a process of polymerizing a linear olefin or a non-linear olefin in
contact with the solid product (II) under polymerizable conditions
thereof. Due to this polymerization treatment, the solid product (II)
results in a condition coated with the resulting polymer.
The above-mentioned reaction of an organoaluminum compound with an electron
donor (B.sub.1) is carried out in a solvent (D) at -20.degree. C. to
+200.degree. C., preferably -10.degree. C. to +100.degree. C., for 30
seconds to 5 hours. The addition order of the organoaluminum compound,
(B.sub.1) and (D) has no particular limitation, and the proportions of
these compounds used are 0.1 to 8 mols, preferably 1 to 4 mols, of the
electron donor (B) and 0 5 to 5 l, preferably 0.5 to 2 l, of the solvent,
each based on one mol of the organoaluminum compound.
Thus, the reaction product (I) is obtained. The product (I) may be
subjected to the succeeding reaction without separating it, that is, in a
solution state, as it is, where the reaction has been completed
(hereinafter referred to often as "reaction solution (I)").
The process of reacting the reaction product (I) with TiCl.sub.4 or an
organoaluminum compound and TiCl.sub.4, followed by subjecting the
resulting solid product (II) to a multi-stage polymerization treatment
with a linear olefin and a non-linear olefin, includes
1 of adding a linear olefin and a non-linear olefin at a multi-stage during
an optional process of the reaction of the reaction product (I) with
TiCl.sub.4 or an organoaluminum compound and TiCl.sub.4 to subject the
solid product (II) to a multi-stage polymerization treatment,
2 a process of adding a linear olefin and a non-linear olefin at a
multi-stage after completion of the reaction of the reaction product (I)
with TiCl.sub.4 or an organoaluminum compound and TiCl.sub.4 to subject
the solid product (II) to a multi-stage polymerization treatment, and
3 a process of after completion of the reaction of the reaction product (I)
with TiCl.sub.4 or an organoaluminum compound and TiCl.sub.4, separating
and removing the resulting liquid portion by filtering-off or decantation,
followed by suspending the resulting solid product (II) in a solvent,
further adding an organoaluminum compound, adding a linear olefin and a
non-linear olefin at a multistage to carry out polymerization treatment
with these olefins.
Further, as to the order of the multi-stage polymerization treatment with a
linear olefin and a non-linear olefin, either one of the linear olefin and
the non-linear olefin may be used in advance, but it is preferred to carry
out polymerization treatment at first with 1 the linear olefin and
successively carry out polymerization treatment with 2 the non-linear
olefin, in the aspect of polymerization operation properties at the time
of using the resulting final titanium trichloride composition and also in
the aspect of the quality of the resulting polyolefin. A linear
olefin-non-olefin block copolymer is formed by the multi-stage
polymerization treatment and the solid product (II) results in a state
where it is coated by the solid product (II).
Further, as described above, in the multi-stage polymerization treatment,
the linear olefin and the non-linear olefin are used each at least once to
thereby obtain the titanium trichloride composition achieving the object
of the present invention, but it is also possible to carry out the
polymerization treatment twice or more, for example, to carry out
polymerization treatment with the non-linear olefin, followed by further
adding 3 the linear olefin to carry out polymerization treatment.
The reaction of the reaction product (I) with TiCl.sub.4 or an
organoaluminum compound and TiCl.sub.4 is carried out at -10.degree. C. to
+200.degree. C., preferably 0.degree. C. to 100.degree. C. for 5 minutes
to 10 hours irrespective of whether a linear olefin and a non-linear
olefin are added or not added during an optional process of the reaction.
It is preferred to use no solvent, but an aliphatic or aromatic hydrocarbon
may be used. Mixing of (I) with TiCl.sub.4 or an organoaluminum compound
and TiCl.sub.4 and with a solvent may be carried out in an optional order,
and addition of a linear olefin and a non-linear olefin may also be
carried out at any stage.
Mixing of the total quantity of (I), TiCl.sub.4, an organoaluminum compound
and a solvent is preferred to be completed within 5 hours, and the
reaction is also carried out during the mixing. After mixing of the total
quantity, it is preferred to further continue the reaction within 5 hours.
The respective quantities of the above materials used for the reaction are
0 to 3,000 ml of the solvent and 0.05 to 10, preferably 0.06 to 0.3 in
terms of the ratio of the number of aluminum atoms in the reaction product
(I) or an organoaluminum compound to the number of Ti atoms in TiCl.sub.4
(Al/Ti), based on one mol of TiCl.sub.4.
As to the polymerization treatment with a linear olefin and a non-linear
olefin, either in the case where a linear olefin and a non-linear olefin
are added during an optional process of the reaction of the reaction
product (I) with TiCl.sub.4 or an organoaluminum compound and TiCl.sub.4,
or in the case where a linear olefin and a non-linear olefin are added
after completion of the reaction of the reaction product (I) with
TiCl.sub.4 or an organoaluminum compound and TiCl.sub.4, the
polymerization treatment is carried out at a multi-stage, under conditions
of a reaction temperature of 0.degree. to 90.degree. C., a reaction time
of one minute to 10 hours and a reaction pressure of the atmospheric
pressure (0 Kgf/cm.sup.2 G)to 10 Kgf/cm.sup.2 G, using 0.1 g to 100 Kg of
a linear olefin and 0.01 g to 100 Kg of a non-linear olefin based on 100 g
of the solid product (II), and so as to give a content of the resulting
linear olefin polymer block in the final solid product (III) i.e. the
titanium trichloride composition of the present invention, of 0.1 to 49.5%
by weight and a content of the resulting non-linear olefin polymer block
therein, of 0.01 to 49.5% by weight, and also a ratio by weight of the
liner olefin polymer block to the non-linear olefin polymer block of 2/98
to 98/2.
If the content of the linear olefin polymer block is less than 0.1% by
weight, the improvement effect in the operational properties at the time
of using the resulting titanium trichloride composition and the effect of
inhibiting the voids of films prepared from the resulting polyolefin are
insufficient, while even if the content exceeds 49.5% by weight,
improvement in these effects is not notable, resulting in operational and
economical disadvantages.
Further, if the content of the non-linear olefin polymer block is less than
0.01% by weight, improvement effect in the transparency of the resulting
films is insufficient, while if it exceeds 49.5% by weight, improvements
in the effects are not notable, resulting in operational and economical
disadvantages.
Further, the ratio by weight of the linear olefin block polymer to the
non-linear olefin polymer block is preferred to be 2/98 to 98/2 in view of
the balance among the improvement effect upon the operational properties,
the inhibition effect upon the voids and the improvement effect upon the
transparency.
In the case where the multi-stage polymerization treatment with a linear
olefin and a non-linear olefin is carried out using the solid product (II)
obtained by reacting the reaction product (I) with TiCl.sub.4 or an
organoaluminum compound and TiCl.sub.4, followed by separating and
removing the resulting liquid portion by filtering off or decantation and
suspending the resulting solid product (II) in a solvent, either
polymerization treatment with a linear olefin or with a non-linear olefin
is carried out at a multi-stage, in the presence of 100 to 5,000 ml of a
solvent and 0.5 to 5,000 g of an organoaluminum compound based on 100 g of
the solid product (II), under reaction conditions of a reaction
temperature of 0.degree. to 90.degree. C., a reaction time of one minute
to 10 hours and a reaction pressure of the atmospheric pressure (0
Kgf/cm.sup.2 G) to 10 Kgf/cm.sup.2 G, using 0.1 g to 100 Kg of a linear
olefin and 0.01 g to 100 Kg of a non-linear olefin based on 100 g of the
solid product (II), and so as to give a content of a linear olefin polymer
block in the final solid product (III) i.e. the titanium trichloride
composition of the present invention, of 0.1 to 49.5% by weight and a
content of a non-linear olefin therein of 0.01 to 49.5% by weight, and a
ratio by weight of the linear olefin polymer block to the non-linear
olefin polymer block of 2/98 to 98/2.
In any of the above-mentioned multi-stage polymerization treatment, after
completion of the polymerization treatments with the linear olefin or the
non-linear olefin at the respective stages, the resulting reaction mixture
may be used, as it is, for the polymerization treatment at the succeeding
stage. Further, it is also possible to remove the coexisting solvent,
unreacted linear olefin or non-linear olefin, organoaluminum compound,
etc. by filtering-off or decantation, followed by again adding a solvent
and an organoaluminum compound and using the resulting material for
polymerization treatment with a non-linear olefin or a linear olefin at
the succeeding stage.
The solvent used at the time of the polymerization treatment is preferred
to be an aliphatic hydrocarbon and the organoaluminum compound may be the
same as or different from that used when the reaction product (I) is
obtained, or that used for direct reaction with TiCl.sub.4 without
reacting with an electron donor (B.sub.1).
After completion of the reaction, the resulting liquid portion is separated
and removed by filtering-off or decantation, followed by repeating washing
with a solvent to obtain a solid product subjected to polymerization
treatment (hereinafter referred to often as solid product (II-A)), which
product may be used in a suspended state in a solvent, as it is, for the
succeeding step or may be further dried and taken out in the form of a
solid material and used.
The solid product (II-A) is then reacted with an electron donor (B.sub.2)
and an electron acceptor (F). This reaction may be carried out without any
solvent, but use of an aliphatic hydrocarbon affords preferable results.
The quantities of these materials used are 0.1 to 1,000 g, preferably 0.5
to 200 g of (B.sub.2), 0.1 to 1,000 g, preferably 0.2 to 500 g of (F) and
0 to 3,000 ml, preferably 100 to 1,000 ml of the solvent, each based on
100 g of the solid product (II-A).
The reaction process includes 1 a process of simultaneously reacting an
electron donor (B.sub.2) and an electron acceptor (F) with the solid
product (II-A), 2 a process of reacting (F) with (II-A), followed by
reacting (B.sub.2), 3 a process of reacting (B.sub.2) with (II-A),
followed by reacting (F) and 4 a process of reacting (B.sub.2) with (F),
followed by reacting (II-A), but any of the processes may be employed.
As to the reaction conditions, 40.degree. to 200.degree. C., preferably
50.degree. to 100.degree. C. and 30 seconds to 5 hours are preferred in
the processes 1 and 2, while in the process 3, (II-A) is reacted with
(B.sub.2) at 0.degree. to 50.degree. C. for one minute to 3 hours,
followed by reacting (F) under the same conditions as in the processes 1
and 2.
Further in the process 4, (B.sub.2) is reacted with (F) at 10.degree. to
100.degree. C. for 30 minutes to 2 hours, followed by cooling down to
40.degree. C. or lower, adding (II-A) and thereafter reacting the mixture
under the same conditions as in the processes 1 and 2.
After completion of the reaction of the solid product (II-A), (B.sub.2) and
(F), the resulting liquid portion is separated and removed by
filtering-off or decantation, followed by repeated washings with a solvent
to obtain a solid product (III) as a titanium trichloride composition for
producing olefin polymers, comprising a linear olefin-non-linear olefin
block copolymer.
The thus obtained solid product (III) i.e. the titanium trichloride
composition of the present invention contains a linear olefin-non-linear
olefin block copolymer in a ratio by weight of a linear olefin polymer
block to a non-linear olefin polymer block of 2/98 to 98/2, the content
of the linear olefin polymer block being 0.1 to 49.5% by weight and that
of the non-linear olefin polymer block being 0.01 to 49.5% by weight, and
is used as a transition metal compound catalyst component for producing
olefin polymers, for olefin polymerization, in combination with at least
an organoaluminum compound.
The organoaluminum compound used for producing the titanium trichloride
composition of the present invention is expressed by the formula
AlR.sup.8.sub.p R.sup.9.sub.p' X.sub.3-(p+p') wherein R.sup.8 and R.sup.9
each represent a hydrocarbon radical such as an alkyl group, a cycloalkyl
group, an aryl group, etc. or an alkoxy group, X represents a halogen atom
and p and p' each represent an optional number satisfying an expression of
0<p+p'.ltoreq.3.
Concrete examples of the organoaluminum compound are trialkylaluminums such
as trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum,
tri-i-hexylaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminum,
tri-n-decylaluminum, etc., dialkylaluminum monohalides such as
diethylaluminum monochloride, di-n-propylaluminum monochloride,
di-i-butylaluminum monochloride, diethylaluminum monofluoride,
diethylaluminum monobromide, diethylaluminum monoiodide, etc.,
dialkylaluminum hydrides such as diethylaluminum hydride, etc., aluminum
sesqui halides such as methylaluminum sesquichloride, ethylaluminum
sesquichloride, etc., and monoalkylaluminum dihalides such as
ethylaluminum dichloride, i-butylaluminum dichloride, etc., and besides,
alkoxyalkylaluminums such as monoethoxydiethylaluminum,
diethoxymonoethylaluminum, etc. may also be used.
These organoaluminum compounds may be used in admixture of two or more
kinds.
As the electron donor used in the present invention, various ones mentioned
below may be exemplified, but ethers are mainly used as (B.sub.1) and
(B.sub.2), and other electron donors are preferred to be used together
with ethers.
Examples of compounds used as the electron donors are organic compounds
having any atoms of oxygen, nitrogen, sulfur and phosphorus such as
ethers, alcohols, esters, aldehydes, aliphatic acids ketones, nitriles,
amines, amides, ureas, thioureas, isocyanates, azo compounds phosphines,
phosphites, phosphinites, hydrogen sulfide, thioethers, thioalcohols, etc.
Concrete examples thereof are ethers such as diethyl ether, di-n-propyl
ether, di-n-butyl ether, diisoamyl ether, di-n-pentyl ether, di-n-hexyl
ether, di-i-hexyl ether, di-n-octyl ether, di-i-octyl ether, di-n-dodecyl
ether, diphenyl ether, ethylene glycol monoethyl ether, tetrahydrofuran,
etc., alcohols or phenols such as methanol, ethanol, propanol, butanol,
pentanol, hexanol, octanol, phenol, cresol, xylenol, ethylphenol,
naphthol, etc., esters such as methyl methacrylate, ethyl acetate, butyl
formate, amyl acetate, vinyl butyrate, vinyl acetate, ethyl benzoate,
propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate,
methyl toluylate, ethyl toluylate, 2-ethylhexyl toluylate, methyl anisate,
ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl
naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate,
ethyl phenylacetate, etc., aldehydes such as acetaldehyde, benzaldehyde,
etc., aliphatic acids such as formic acid, acetic acid, propionic acid,
butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, etc.,
aromatic acids such as benzoic acid, ketones such as methyl ethyl ketone,
methyl isobutyl ketone, benzophenone, etc., nitrile acids such as
acetonitrile, etc., amines such as methylamine, diethylamine,
tributylamine, triethanolamine, .beta.-(N,N-dimethylamino)ethanol,
pyridine, quinoline, .alpha.-picoline, 2,4,6-trimethylpyridine,
N,N,N',N'-tetramethylethylenediamine, aniline, dimethylaniline, etc.,
amides such as formamide, hexamethylphosphoric acid triamide,
N,N,N',N',N"-pentamethyl-N'-.beta.-dimethylaminomethylphosphoric acid
triamide, octamethylpyrophosphoroamide, etc., ureas such as
N,N,N',N'-tetramethylurea, etc., isocyanates such as phenyl isocyanate,
toluyl isocyanate, etc., azo compounds such as azobenzene, etc.,
phosphines such as ethylphosphine, triethylphosphine,
tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine,
triphenylphosphine oxide, etc., phosphites such as dimethyl phosphite,
di-n-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, triphenyl
phosphite, etc., phosphinites such as ethyldiethyl phosphinite, ethylbutyl
phosphinite, phenyldiphenyl phosphinite, etc., thioethers such as diethyl
thioether, diphenyl thioether, methyl phenyl thioether, ethylene sulfide,
propylene sulfide, etc., thioalcohols such as ethyl thioalcohol, n-propyl
thioalcohol, thiophenol, etc.
These electron donors may be used in admixture. The electron donor
(B.sub.1) used for obtaining the reaction product (I) and (B.sub.2)
reacted with the solid product (II-A) may be either same or different.
The electron acceptor (F) used in the present invention is represented by
halides of elements of Groups III to VI of the Periodic Table. Concrete
examples thereof are anhydrous aluminum chloride silicon tetrachloride,
stannous chloride, stannic chloride, titanium tetrachloride, zirconium
tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium
tetrachloride, antimony pentachloride, etc. and these may be used in
admixture. Titanium tetrachloride is most preferred.
As the solvent, the following may be used:
aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane,
i-octane, etc., halogenated hydrocarbons used in place of or together with
aliphatic hydrocarbons, such as carbon tetrachloride, chloroform,
dichloroethane, trichloroethylene, tetrachloroethylene, etc., aromatic
hydrocarbons such as napthalene, etc., alkyl derivatives thereof such as
mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene,
1-phenylnaphthalene, halides thereof such as monochlorobenzene,
chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene,
bromobenzene, etc.
Examples of the linear olefin used for the polymerization treatment in the
present invention are ethylene, propylene, butene-1, pentene-1, hexene-1,
etc., and ethylene and propylene are preferably used. These linear olefins
may be used alone or in admixture.
The non-linear olefin used for the polymerization treatment in the present
invention is as follows:
1 saturated ring-containing hydrocarbon monomers of 3 to 18 carbon atoms
expressed by the formula CH.sub.2 .dbd.CH--R.sup.1 wherein R.sup.1
represents a saturated ring-containing hydrocarbon monomer which has a
saturated ring-containing structure of a hydrocarbon which may contain
silicon and may contain silicon;
2 branched olefins expressed by the formula
##STR11##
wherein R.sup.2 represents a linear hydrocarbon radical of 1 to 3 carbon
atoms which may contain silicon or silicon, R.sup.3, R.sup.4 and R.sup.5
each represent a linear hydrocarbon radical of 1 to 6 carbon atoms which
may contain silicon, but either one of R.sup.3, R.sup.4 and R.sup.5 may be
hydrogen atom; and
3 aromatic monomers expressed by the formula
##STR12##
wherein n represents 0 or 1, m represents 1 or 2, R.sup.6 represents a
linear hydrocarbon radical of 1 to 6 carbon atoms which may contain
silicon and R.sup.7 represents a hydrocarbon radical of 1 to 12 carbon
atoms which may contain silicon, hydrogen atom or a halogen atom and when
m represents 2, the respective R.sup.7 s may be the same or different.
Concrete examples of the saturated ring-containing hydrocarbon monomers 1
are vinylcycloalkanes such as vinylcyclopropane, vinylcyclobutane,
vinylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane,
2-methylvinylcyclohexane, 3-methylvinylcyclohexane,
4-methylvinylcyclohexane, vinylcycloheptane, etc., allylcycloalkanes such
as allylcyclopentane, allylcyclohexane, etc., and besides, saturated
ring-containing hydrocarbon monomers having silicon atom in the saturated
ring-structure such as cyclotrimethylenevinylsilane,
cyclotrimethylenemethylvinylsilane, cyclotetramethylenevinylsilane,
cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane,
cyclopentamethyleneethylvinylsilane, cyclohexamethylenevinylsilane,
cyclohexamethylenemethylvinylsilane, cyclohexamethyleneethylvinylsilane,
cyclotetramethyleneallylsilane, cyclotetramethylenemethylallylsilane,
cyclopentamethyleneallylsilane, cyclopentamethylenemethylallylsilane,
cyclopentamethyleneethylallylsilane, etc., saturated ring-containing
hydrocarbon monomers having silicon atom outside the saturated ring
structure such as cyclobutyldimethylvinylsilane,
cyclopentyldimethylvinylsilane, cyclopentylethylmethylvinylsilane,
cyclopentyldiethylvinylsilane, cyclohexylvinylsilane,
cyclohexyldimethylvinylsilane, cyclohexylethylmethylvinylsilane,
cyclobutyldimethylallylsilane, cyclopentyldimethylallylsilane,
cyclohexylmethylallylsilane, cyclohexyldimethylallylsilane,
cyclohexylethylmethylallylsilane, cyclohexyldiethylallylsilane,
4-trimethylsilylvinylcyclohexane, 4-trimethylsilylallylcyclohexane, etc.
Concrete examples of the branched olefins 2 are 3-position-branched olefins
such as 3-methylbutene-1, 3-methylpentene-1, 3-ethylpentene-1, etc.,
4-position-branched olefins such as 4-ethylhexene-1,
4,4-dimethyl-pentene-1, 4,4-dimethylhexene-1, etc., alkenylsilanes such as
vinyltrimethylsilane, vinyltriethylsilane, vinyltri-n-butylsilane,
allyltrimethylsilane, allylethyldimethylsilane, allyldiethylmethylsilane,
allyltriethylsilane, allyl-n-propylsilane, 3-butenyltrimethylsilane,
3-butenyltriethylsilane, etc., diallylsilanes such as
dimethyldiallylsilane, ethylmethyldiallylsilane, diethyldiallylsilane,
etc.
Further, concrete examples of the aromatic monomers 3 are styrene, as its
derivatives, alkylstyrenes such as o-methylstyrene, p-t-butylstyrene,
dialkylstyrenes such as 2,4-dimethylstyrene, 2,5-dimethylstyrene,
3,4-dimethylstyrene, 3,5-dimethylstyrene, etc., halogen-substituted
styrenes such as 2-methyl-4-fluorostyrene, 2-ethyl-4-chlorostyrene,
o-fluorostyrene, p-fluorostyrene, etc., trialkylsilylstyrenes such as
p-trimethylsilylstyrene, m-triethylsilylstyrene,
p-ethyldimethylsilylstyrene, etc., allyltoluenes such as o-allyltoluene,
p-allyltoluene, etc., allylxylenes such as 2-allyl-p-xylene,
4-allyl-o-xylene, 5-allyl-m-xylene, etc., alkenylphenylsilanes such as
vinyldimethylphenylsilane, vinylethylmethylphenylsilane,
vinyldiethylphenylsilane, allyldimethylphenylsilane,
allylethylmethylphenylsilane, etc., 4-(o-tolyl)-butene-1,
1-vinylnaphthalene, etc. These non-linear olefins may be used alone or in
admixture.
The thus obtained titanium trichloride composition of the present invention
is combined with at least an organoaluminum compound and used as a
catalyst for olefin polymerization in a conventional manner, or further
preferably the composition is reacted with an olefin and the resulting
preactivated catalyst is used for olefin polymerization.
As the organoaluminum compound used for olefin polymerization,
organoaluminum compounds same as those used when the above titanium
trichloride composition of the present invention is prepared may be used.
The organoaluminum compounds may be the same as or different from those
used when the titanium trichloride composition is prepared.
Further, examples of olefins used for the above preactivation are linear
monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1,
heptene-1, etc., and branched monoolefins such as 4-methyl-pentene-1,
2-methyl-pentene-1, etc.
These olefins may be same as or different from those as the object of the
polymerization, and two kinds or more of olefins may be used in admixture.
The polymerization form in which the above catalyst is used has no
particular limitation, but not only liquid phase polymerization such as
slurry polymerization or bulk polymerization, but also even gas phase
polymerization may be preferably carried out.
In the case of slurry polymerization or bulk polymerization, even a
catalyst having the titanium trichloride composition combined with an
organoaluminum compound exhibits a sufficient effect, but in the case of
gas phase polymerization, a preactivated catalyst obtained by reacting an
olefin is preferred.
In the case where slurry polymerization or bulk polymerization is followed
by gas phase polymerization, even if the initially used catalyst is the
former catalyst, an olefin reaction has already been carried out in the
case of gas phase polymerization; hence the catalyst constitutes the same
as in the latter one and exhibits a superior effect.
In the preactivation, 0.005 to 500 g of an organoaluminum, 0 to 50 l of a
solvent, 0 to 1,000 ml of hydrogen and 0.05 to 5,000 g, preferably 0.05 to
3,000 g of an olefin, each based on 1 g of the titanium trichloride
composition are used. An olefin is reacted at 0.degree. to 100.degree. C.
for one minute to 20 hours, and it is preferred to react 0.01 to 2,000 g,
preferably 0.05 to 200 g of an olefin per g of the titanium trichloride
composition.
The preactivation may be carried out in a hydrocarbon solvent such as
propane, butane, n-pentane, n-hexane, n-heptane, benzene, toluene, etc.,
and also may be carried out in a liquefied olefin such as liquefied
propylene, liquefied butene-1, etc. or in gaseous ethylene or propylene,
and further, may be carried out in the coexistence of hydrogen.
The preactivation may be carried out in the coexistence of polymer
particles obtained in advance by slurry polymerization or bulk
polymerization or gas phase polymerization. The polymer may be same as or
different from the olefin polymer as the object of the polymerization. The
quantity of the polymer particles capable of being made coexistent is in
the range of 0 to 5,000 g per g of the titanium trichloride composition.
The solvent or olefin used in the preactivation may be removed midway
during the preactivation or after completion of the preactivation by
distilling-off under reduced pressure or filtering-off, and in order to
suspend the solid product in a solvent in a quantity not exceeding 80 l
per g of the product, a solvent may be added.
The preactivation process includes various embodiments as follows:
1 a process of carrying out slurry reaction, bulk reaction or gas phase
reaction in contact of an olefin with a catalyst having the titanium
trichloride composition combined with an organoaluminum compound;
2 a process of combining the titanium trichloride composition with an
organoaluminum compound in the presence of an olefin;
3 process of making an olefin polymer coexistent in the process 1 or 2; and
4 a process of making hydrogen coexistent in the process 1, 2 or 3.
There is no essential difference between bringing the catalyst into a
slurry state and bringing it into powder.
The catalyst consisting of the titanium trichloride composition and an
organoaluminum compound combined together as described above, or the
catalyst further preactivated with an olefin is used for producing olefin
polymers, and it is also possible to add an electron donor as a third
component of the catalyst in order to improve its stereoregularity and use
the resulting catalyst for polymerization, as in conventional olefin
polymerization.
The quantities of the respective catalyst components used are similar to
those in conventional olefin polymerization, and concretely, 0.01 to 500 g
of an organoaluminum compound and 0 to 200 g of an electron donor per g of
the titanium trichloride composition are used.
The polymerization form of polymerizing olefin includes, as described
above, 1 slurry polymerization carried out in a hydrocarbon solvent such
as n-pentane, n-hexane, n-heptane, n-octane, benzene, toluene, etc., 2
bulk polymerization carried out in a liquefied olefin such as liquefied
propylene, liquefied butene-1, etc., 3 gas phase polymerization carried
out in a gas phase of an olefin such as ethylene, propylene, etc. and 4 a
process of stepwise combining two or more of the above processes 1 to 3.
In any cases, polymerization is carried out at a polymerization temperature
of room temperature (20.degree. C.) to 200.degree. C., under a
polymerization pressure of the atmospheric pressure (0 Kg/cm.sup.2 G) to
50 Kg/cm.sup.2 G and usually for about 5 minutes to 20 hours.
In the polymerization, a suitable quantity of hydrogen is added for
controlling the molecular weight, as in conventional polymerization
process.
Examples of olefins subjected to polymerization are linear monoolefins such
as ethylene, propylene, butene-1, hexene-1, octene-1, etc., branched
monoolefins such as 4-methylpentene-1, 2-methylpentene-1, etc., diolefins
such as butadiene, isoprene, chloroprene, etc., and homopolymerization of
these olefins is not only carried out, but also copolymerization of these
olefins with each other or one another, for example, propylene with
ethylene, butene-1 with ethylene, propylene with butene-1, etc., propylene
with ethylene and butene-1, etc. (combination of three components) is
carried out, and further it is also possible to carry out block
copolymerization by varying kinds of olefins fed in a multi-stage
polymerization.
Next, the constitutions of the present invention described in the above
items (10) to (18) will be described in more detail.
The titanium catalyst component for olefin polymerization of the present
invention is directed to a supported type titanium catalyst component
comprising a linear olefin-non-linear olefin block copolymer (hereinafter
often abbreviated to a specified block copolymer) containing at least one
linear olefin polymer block and at least one non-linear olefin polymer
block and titanium, magnesium, a halogen and an electron donor as
indispensable components, and a process for producing the supported type
titanium catalyst component will be described below.
The supported type titanium catalyst component referred to herein means a
titanium catalyst component supported on a carrier.
Further, the "liquefaction" of magnesium compound referred to herein
includes not only a case where the compound itself forms a liquid, but
also a case where the compound itself is soluble in a solvent to form a
solution and a case where the compound reacts with another compound or
forms a complex therewith so that the resulting material is solubilized in
a solvent to form a solution. Further, the solution may be that in a state
where a colloid form or semi-dissolved form substance is contained,
besides that in a state where the compound is completely dissolved.
As the magnesium compound to be liquefied, it may be any of those which
form the above-mentioned "liquefied" state. Examples of such compounds are
magnesium dihalides, alkoxymagnesium halides, aryloxymagnesium halides,
dialkoxymagnesiums, diaryloxymagnesiums, magnesium oxyhalides, magnesium
oxide, magnesium hydroxide, magnesium carboxylates, dialkylmagnesiums,
alkylmagnesium halides, etc., and besides, metal magnesium may also be
used. Further, besides these magnesium compounds or metal magnesium,
reaction products thereof with an electron donor, a silicon compound or an
aluminum compound may also be used.
As a process for liquefying magnesium compounds, known processes may be
employed. Examples thereof are a process of liquefying magnesium compounds
with an alcohol, an aldehyde, an amine or a carboxylic acid (Japanese
patent application laid-open No. Sho 56-811/1981), a process of liquefying
with an o-titanic acid ester (Japanese patent application laid-open No.
Sho 54-40,293/1979), a process of liquefying with a phosphorus compound
(Japanese patent application laid-open No. Sho 58-19,307/1983), and
combinations of these processes, etc. Further, as to organomagnesium
compounds having a C-Mg bond which cannot be applied to the above
processes, since the compounds are soluble in ether, dioxane, pyridine,
etc., they may be used in the form of solution thereof in such solvents,
or they may be reacted with an organometal compound to form a complex
compound expressed by the formula M.sub.p Mg.sub.q R.sup.10.sub.r
R.sup.11.sub.s (wherein M represents Al, Zn, B or Be atom, R.sup.10 and
R.sup.11 each represent a hydrocarbon radical, p, q, r and s each are
larger than 0 and when the valency of M is denoted by v, then r, s, v, p
and q have a relationship of r+s=vp+2q) (Japanese patent application
laid-open No. Sho 50-139,885/1975), followed by dissolving the complex
compound in a hydrocarbon solvent to effect liquefaction.
Further, in the case where metal magnesium is used, liquefaction may be
carried out according to a process of liquefying it with an alcohol and an
o-titanic acid ester (Japanese patent application laid-open No. Sho
51-51,587/1975) or a process of reacting it with a halogenated alkyl in
ether to form the so-called Grignard reagent.
Among the above-mentioned processes of liquefying a magnesium compound, for
example, a case where magnesium chloride is dissolved in an inert
hydrocarbon solvent (D.sub.1) using a titanic acid ester and an alcohol
will be illustrated.
0.1 to 2 Mols of a titanic acid ester, 0.1 to 5 mols of an alcohol and 0.1
to 5 l of a solvent (D.sub.1) each per mol of magnesium chloride are mixed
in an optional addition order, followed by heating the resulting
suspension with stirring to 40.degree. to 200.degree. C., preferably
50.degree. to 150.degree. C. The time required for the reaction and
dissolution is 5 minutes to 7 hours, preferably 10 minutes to 5 hours.
The titanic acid ester refers to an o-titanic acid ester expressed by
Ti(OR.sup.12).sub.4 and a polytitanic acid ester expressed by R.sup.13
--Ti(OR.sup.14)(OR.sup.15).sub.t OR.sup.16 wherein R.sup.12, R.sup.13,
R.sup.14, R.sup.15 and R.sup.16 each represent an alkyl group of 1 to 20
carbon atoms or a cycloalkyl group of 3 to 20 carbon atoms and t
represents an integer of 2 to 20.
Concrete examples thereof are o-titanic acid esters such as methyl
o-titanate, ethyl o-titanate, n-propyl o-titanate, i-propyl o-titanate,
n-butyl o-titanate, i-butyl o-titanate, n-amyl o-titanate, 2-ethylhexyl
o-titanate, n-octyl o-titanate, phenyl o-titanate, cyclohexyl o-titanate,
etc. and polytitanic acid esters such as methyl polytitanate, ethyl
polytitanate, n-propyl polytitanate, i-propyl polytitanate, n-butyl
polytitanate, i-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl
polytitanate, n-octyl polytitanate, phenyl polytitanate, cyclohexyl
polytitanate, etc. The quantity of the polytitanic acid ester used may be
that corresponding to the o-titanic acid ester as calculated in terms of
o-titanic acid ester units.
As the alcohol, aliphatic saturated or unsaturated alcohols may be used.
Concrete examples are monohydric alcohols such as methanol, ethanol,
n-propanol, i-propanol, n-butanol, n-amyl alcohol, i-amyl alcohol,
n-hexanol, n-octanol, 2-ethylhexanol, allyl alcohol, etc. and polyhydric
alcohols such as ethylene glycol, trimethylene glycol, glycerine, etc.
Among these, aliphatic saturated alcohols of 4 to 10 carbon atoms are
preferred.
Examples of the inert hydrocarbon solvent (D.sub.1) are aliphatic
hydrocarbons such as pentane, hexane, heptane, nonane, decane, kerosine,
etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc.,
halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane,
1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene, etc. Among these,
aliphatic hydrocarbons are preferred.
The solid product (I) is obtained by contacting the above liquefied
magnesium compound with a depositing agent (X.sub.1), a halogenated
compound (X.sub.2), an electron donor (B.sub.1) and a titanium compound
(T.sub.1). Examples of the depositing agent (X.sub.1) are halogenating
agents such as halogens, halogenated hydrocarbons, halogen-containing
silicon compounds, halogen-containing aluminum compounds,
halogen-containing titanium compounds, halogen-containing zirconium
compounds, halogen-containing vanadium compounds, etc.
Further, in the case where the liquefied magnesium compounds are the
above-mentioned organomagnesium compounds, it is also possible to use
active hydrogen-containing compounds such as alcohols, Si-H
bond-containing polysiloxanes, etc. The quantity of these depositing
agents (X.sub.1) used is 0.1 to 50 mols per mol of magnesium compounds.
Further, examples of the halogen compound (X.sub.2) are halogens and
halogen-containing compounds, and compounds similar to the halogenating
agents illustrated as examples of the depositing agent are usable, and in
the case where halogenating agents are used as the depositing agent, 1 it
is not always necessary to newly use the halogen compound (X.sub.2). The
quantity of the halogen compound (X.sub.2) used is 0.1 to 50 mols per mol
of the magnesium compound.
Examples of the electron donor (B.sub.1) are oxygen-containing electron
donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids,
organic or inorganic acid esters, ethers, acid amides, acid anhydrides,
etc., nitrogen-containing electron donors such as ammonia, amines,
nitriles, isocyanates, etc., and phosphorus-containing electron donors
such as phosphines, phosphites, phosphinites, etc.
Concrete examples are alcohols such as methanol, ethanol, n-propanol,
i-propanol, n-butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl
alcohol, benzyl alcohol, ethylene glycol, glycerine, etc., phenols such as
phenol, cresol, xylenol, ethylphenol, etc., ketones such as acetone,
methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone,
etc., aldehydes such as acetaldehyde, propionaldehyde, benzaldehyde, etc.,
carboxylic acids such as formic acid, acetic acid, propionic acid, butyric
acid, valeic acid, etc., aliphatic carboxylic acid esters such as methyl
formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate,
n-propyl acetate, i-propyl acetate, n-butyl acetate, octyl acetate, phenyl
acetate, ethyl propionate, etc., aromatic monocarboxylic acid esters such
as methyl benzoate, ethyl benzoate, methyl toluylate, ethyl toluylate,
methyl anisate, ethyl anisate, phenyl anisate, etc., aromatic polybasic
carboxylic acid esters such as monomethyl phthalate, dimethyl phthalate,
diethyl phthalate, di-n-propyl pthalate, mono-n-butyl phthalate,
di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate,
di-2-ethylhexyl phthalate, di-n-octyl phthalate, diethyl isophthalate,
dipropyl isophthalate, dibutyl isophthalate, di-2-ethylhexyl isophthalate,
diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate,
di-i-butyl naphthalenecarboxylate, etc., ethers such as methyl ether,
ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran,
anisole, diphenyl ether, etc., acid amides such as acetic acid amide,
benzoic acid amide, toluic acid amide, etc., acid anhydrides such as
acetic anhydride, maleic anhydride benzoic anhydride, phthalic anhydride,
tetrahydrophthalic anhydride, etc., amines such as ethylamine,
tributylamine, aniline, pyridine, picoline, tetramethylethylenediamine,
etc., nitriles such as acetonitrile, benzonitrile, etc., phosphines such
as ethylphosphine, triethylphosphine, tri-n-butylphosphine,
triphenylphosphine, etc., phosphites such as dimethylphosphite,
triethylphosphite, triphenylphosphite, etc., phosphinites such as
ethyldiethylphosphinite, ethylbutylphosphinite, etc., alkoxysilanes such
as tetraethoxysilane, tetrabutoxysilane, etc., and preferably, aromatic
monocarboxylic acid esters, aromatic polybasic carboxylic acid esters and
alkoxysilanes, and more preferably, aromatic polybasic carboxylic acid
esters are used.
As to these electron donors (B.sub.1), one or more kinds are used and the
quantity thereof used is 0.01 to 5 mols per mol of the magnesium compound.
As the titanium compound (T.sub.1) necessary for preparing the solid
product (I), there are used halogenated titanium compounds expressed by
the formula Ti(OR.sup.17).sub.4-u X.sub.u wherein R.sup.17 represents an
alkyl group, a cycloalkyl group or an aryl group, X represents a halogen
atom and u represents
an optional number satisfying an expression of 0<u.ltoreq.4, and o-titanic
acid esters and polytitanic acid esters illustrated at the time of the
above-mentioned liquefaction of magnesium compounds.
Concrete examples of the halogenated titanium compounds are TiCl.sub.4,
TiBr.sub.4, methoxytitanium trichloride, ethoxytitanium trichloride,
propoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium
trichloride, ethoxytitanium tribromide, butoxytitanium tribromide,
dimethoxytitanium dichloride, diethoxytitanium dichloride,
dipropoxytitanium dichloride, dibutoxytitanium dichloride,
diphenoxytitanium dichloride, diethoxytitanium dibromide, dibutoxytitanium
dibromide, trimethoxytitanium chlofide, triethoxytitanium chloride,
tributoxytitanium chloride, triphenoxytitanium chloride, etc.
As the o-titanic acid esters and polytitanic acid esters, the same as those
already mentioned are exemplified. As to these titanium compounds
(T.sub.1), one or more kinds are used, and in the case where halogenated
titanium compounds are used as the titanium compound (T.sub.1), since they
contain a halogen, the depositing agent (X.sub.1) and the halogenated
compound (X.sub.2) are optionally used.
Further, in the case where a titanic acid ester is used at the time of
liquefying the magnesium compound, new use of the titanium compound
(T.sub.1) is also optional. The quantity of the titanium compound
(T.sub.1) used is 0.1 to 100 mols per mol of the magnesium compound.
The above-mentioned liquefied magnesium compound, depositing agent
(X.sub.1), halogenated compound (X.sub.2), electron donor (B.sub.1) and
titanium compound (T.sub.1) are contacted with stirring to obtain the
solid product (I). At the time of the contact, an inert hydrocarbon
(D.sub.2) may be used and the respective components may be diluted in
advance and used.
As the inert hydrocarbon solvent (D.sub.2), those similar to the above
(D.sub.1) may be illustrated. The quantity thereof used is 0 to 5,000 ml
per mol of the magnesium compound.
The process of the contact includes various ones such as
1 a process of adding (X.sub.1) to a liquefied magnesium compound to
deposit solids and contacting (X.sub.2), (B.sub.1) and (T.sub.1) with the
solids in an optional order; 2 a process of adding (X.sub.1) to a solution
obtained by contacting a liquefied magnesium compound with (B.sub.1) to
deposit solids and contacting (X.sub.2) and (T.sub.1) with the solids in
an optional order, 3 a process of contacting a liquefied magnesium
compound with (T.sub.1), followed by adding (X.sub.1) and further
contacting (B.sub.1) and (X.sub.2) with the mixture in an optional order,
or the like processes.
While the quantities of the respective components used are in the
above-mentioned ranges, these components may be used at a time or at
several separated stages. Further, in the case where one component
contains an atom or a group characterizing another component, as already
described above, it is not always necessary to newly use the other
component. For example, in the case where a titanic acid ester is used at
the time of liquefying a magnesium compound, (T.sub.1) constitutes an
optional component to be used, and similarly, in the case where a
halogen-containing titanium compound is used as the depositing agent
(X.sub.1), (X.sub.2) and (Ti) constitute optional components to be used,
and in the case where a halogenating agent is used as the depositing agent
(X.sub.1), (X.sub.2) constitutes an optional component to be used.
The contact temperature of the respective components is -40.degree. to
+180.degree. C., preferably -20.degree. to +150.degree. C., and the
contact time thereof is 5 minutes to 8 hours, preferably 10 minutes to 6
hours at each stage, under the atmospheric pressure to 10 Kg/cm.sup.2 G.
A solid product (I) is obtained in the above contact reaction. The solid
product (I) may be successively subjected to the subsequent stage, but it
is preferred to wash the product with an inert solvent as already
mentioned, in advance.
The solid product (I) obtained according to the above process is then
subjected to a multi-stage polymerization treatment with 1 a linear olefin
and 2 a non-linear olefin in the presence of an organoaluminum compound
(AL.sub.1) to obtain a solid product (II).
As to this multi-stage polymerization treatment, either one of the linear
olefin or the non-linear olefin may be used in advance, but it is
preferred to subject the product to the polymerization treatment first
with 1 the linear olefin and successively with 2 the non-linear olefin, in
the aspect of the polymerization operation properties at the time of use
of the resulting final titanium catalyst component as well as in the
aspect of the quality of the resulting olefin polymer. A linear
olefin-non-linear olefin block copolymer is formed by the multi-stage
polymerization treatment, and the solid product (I) results in a state
where it is coated with the block copolymer.
In order to obtain the titanium catalyst component achieving the object of
the present invention, the multistage polymerization treatment may be
carried out each at least once using each of the linear olefin and the
non-linear olefin, as described above, but it is also possible to carry
out the polymerization treatment twice or more, for example, by carrying
out polymerization treatment with the non-linear olefin, followed by
further adding 3 a linear olefin to carry out polymerization treatment.
As to the conditions of the multi-stage polymerization treatment, adding
100 to 5,000 ml of an inert hydrocarbon solvent (D.sub.3) and 0.5 to 5,000
g of an organoaluminum compound (AL.sub.1) to 100 g of a solid product
(I), under conditions of a reaction temperature of 0.degree. to 90.degree.
C., a reaction time of one minute to 10 hours and a reaction pressure of
the atmospheric pressure (0 Kgf/cm.sup.2 G) to 10 Kgf/cm.sup.2 G, and
using 0.1 g to 100 Kg of a linear olefin and 0.01 g to 100 Kg of a
non-linear olefin per 100 g of the solid product (II), a multi-stage
polymerization treatment is carried out so as to give a content of the
linear olefin polymer block in the final solid product (III), i.e. the
supported type titanium catalyst component, of 0.1 to 49.5% by weight and
a content of the non-linear olefin polymer block therein of 0.01 to 49.5%
by weight, and so as to give a ratio by weight of the linear olefin
polymer block to the non-linear olefin polymer block, of 2/98 to 98/2.
If the content of the linear olefin polymer block is less than 0.1% by
weight, improvement in the operation properties at the time of using the
resulting titanium catalyst component as well as the effect of inhibiting
the resulting olefin polymer from forming voids are both insufficient,
while even if it exceeds 49.5% by weight, improvement in the effects is
not notable, resulting in operational and economical disadvantages.
Further, if the content of the non-linear olefin polymer block is less than
0.01% by weight, the effect of improving the transparency, when the
resulting polymer is made into film, is insufficient, while if it exceeds
49.5% by weight, improvement in the effects is not notable, resulting in
operational and economical disadvantages.
Further, the ratio by weight of the linear olefin polymer block to the
non-linear olefin block is preferred to be 2/98 to 98/2, in the aspect of
balance between the improvement effect of the operation properties and
that of the transparency.
In addition, in the above multi-stage polymerization treatment, after the
polymerization treatment with the linear olefin or the non-linear olefin
at the respective stages has been completed, it is possible to use the
resulting reaction mixture, as it is, for the polymerization treatment at
the subsequent stage. Further, it is also possible to remove the
coexisting solvent, unreacted linear olefin or non-linear olefin and
organoaluminum compound (AL.sub.1), etc. by filtering off or decantation,
again add a solvent and an organoaluminum compound (AL.sub.1) and use the
resulting mixture for polymerization treatment with a non-linear olefin or
a linear olefin at the succeeding stage.
Further, at the stage of the polymerization treatment, it is also possible
to make coexistent a carboxylic acid ester such as ethyl benzoate, methyl
toluylate, ethyl anisate, etc. or an electron donor (B.sub.2) represented
by phenyltriethoxysilane, diphenyldimetooxysilane, methyltriethoxysilane,
etc. The quantity thereof used is 0 to 5,000 g per 100 g of the solid
product (I).
The organoaluminum compound (AL.sub.1) used for the polymerization
treatment is expressed by the formula AlR.sup.8.sub.l R.sup.9.sub.l
X.sub.3-(l+l') wherein R.sup.8 and R.sup.9 each represent a hydrocarbon
radical such as an alkyl group, a cycloalkyl group, an aryl group, etc., X
represents a halogen atom and l and l' each represent an optional number
satisfying an expression of 0<l+l'.ltoreq.3. Its concrete examples are the
same as those described above in the inventions of the items (1) to (9) of
the present invention.
These organoaluminum compounds may be used in admixture of two kinds or
more.
As the solvent (D.sub.3), inert hydrocarbon solvents same as the (D.sub.1)
and (D.sub.2) already mentioned may be illustrated.
Examples of the linear olefin used for the polymerization treatment of the
present invention are those such as ethylene, propylene, butene-1,
pentene-1, hexene-1, etc. and particularly, ethylene and propylene are
preferably used. These linear olefins may be used alone or in admixture.
The non-linear olefin, branched olefin and armatic monomer used for the
polymerization treatment in the inventions of the above items (10) to (18)
of the present invention are the same as described in the above items (1)
to (9) of the present invention.
As described above, the multi-stage polymerization treatment is carried out
with a linear olefin and a non-linear olefin and the resulting material is
washed with an inert hydrocarbon solvent as already mentioned to obtain
the solid product (II).
Successively, a halogenated titanium compound (T.sub.2) is reacted with the
solid product (II) to obtain a titanium catalyst component containing a
specified silicon-containing polymer. As the halogenated titanium compound
(T.sub.2), there is used a halogenated titanium compound expressed by the
formula Ti(OR.sup.17).sub.4-u X.sub.u (wherein R.sup.17 represents an
alkyl group, a cycloalkyl group or an aryl group, X represents a halogen
atom and u represents an optional number satisfying an expression of
0<u.ltoreq.4), as illustrated above as an example of the titanium compound
(T.sub.1) necessary for preparing the solid product (I). As its concrete
examples, similar compounds may also be illustrated, and TiCl.sub.4 is
most preferred.
The reaction of the solid product (II) with the halogenated titanium
compound (T.sub.2) is carried out using one mol or more of the halogenated
titanium compound (T.sub.2) per mol of a magnesium compound in the solid
product (II), under conditions of a reaction temperature of 20.degree. to
200.degree. C. and a reaction pressure of the atmospheric pressure to 10
Kg/cm.sup.2 G and for 5 minutes to 6 hours, preferably 10 minutes to 5
hours. Further, it is also possible to carry out the reaction in the
presence of an inert hydrocarbon solvent (D.sub.4) and an electron donor
(B.sub.3), and concretely, an inert solvent and an electron donor same as
in the (D.sub.1) to (D.sub.3) and (B.sub.1) already mentioned are used.
The quantities thereof used are preferred to be 0 to 5,000 ml of (D.sub.4)
per 100 g of the solid product (II) and 0 to 2 mols per mol of (B.sub.3)
per mol of the magnesium compound in the solid product (II). After the
reaction of the solid product (II) with the halogenated titanium compound
(T.sub.2) and if necessary, further with an electron donor, the resulting
solids are separated by filtering-off or decantation, followed by washing
with an inert hydrocarbon solvent and removing unreacted substances or
byproducts to obtain the solid product (III).
Thus, there is obtained the solid product (III) i.e. the supported type
titanium catalyst component used for producting olefin polymers, of the
present invention, comprising a linear olefin-non-linear olefin block
copolymer in a ratio by weight of the linear olefin polymer block to the
non-linear olefin polymer block of 2/98 to 98/2 and containing 0.1 to
49.5% by weight of the linear olefin polymer block and 0.01 to 49.5% by
weight of the non-linear olefin polymer block and Ti, Mg, a halogen atom
and an electron donor as indispensable components.
The thus obtained titanium catalyst component containing a specified block
copolymer, of the present invention can be used in the same manner as in
known titanium catalyst components used for producing olefin polymers.
The titanium catalyst component containing a specified block copolymer is
combined with an organoaluminum compound (AL.sub.2) and an electron donor
(B.sub.4) to prepare a catalyst, or further a small quantity of an olefin
is polymerized on the catalyst to prepare a preactivated catalyst, and the
catalysts are then used for olefin polymerization.
As the organoaluminum compound (AL.sub.2) used for the olefin
polymerization, organoaluminum compounds same as (AL.sub.1) used for
obtaining the above-mentioned titanium catalyst component of the present
invention may be used. Further, as the electron donor (B.sub.4), organic
acid esters, organosilicon compounds containing a Si-O-C bond such as
alkoxysilanes, aryloxysilane compounds, etc., ethers, ketones, acid
anhydrides, amines, etc. are preferably used.
Besides the compounds illustrated as electron donors (B.sub.1) to (B.sub.3)
used for producing the above-mentioned titanium catalyst component, the
following concrete examples are mentioned:
amines having a large steric hindrance such as
2,2,6,6-tetramethylpiperidine, 2,2,5,5-tetramethylpyrrolidine,
organosilicon compounds having a Si-O-C bond such as
trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,
dimethyldiethoxysilane, diphenyldimethoxysilane,
methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltriethoxysilane,
methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane,
methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
butyltriethoxysilane, phenyltriethoxysilane, ethyltri-i-propoxysilane,
vinyltriacetoxysilane, etc.
The quantities of the respective catalyst components used are the same as
those in the case of conventional olefin polymerization, and are
concretely about 0.05 to 500 g of organoaluminum compound (AL.sub.2) and
about 0.01 to 200 g of electron donor (B.sub.4) each per g of the titanium
catalyst component.
Further, examples of olefins used for the preactivation are linear
monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1,
heptene-1, etc., branched monoolefins such as 4-methyl-pentene-1,
2-methyl-pentene-1, etc.
These olefins may be same as or different from those as the object of the
polymerization and may be used in admixture of two kinds or more.
The form of polymerization using the above catalyst has no particular
limitation, but not only liquid phase polymerization such as slurry
polymerization and bulk polymerization, but also gas phase polymerization
may be preferably carried out.
In the case of slurry polymerization or bulk polymerization, even a
combined catalyst of the titanium catalyst component with organoaluminum
compound (AL.sub.2) and electron donor (B.sub.4) exhibits a sufficient
effectiveness, but in the case of gas phase polymerization, a preactivated
catalyst obtained by reacting olefin is preferred.
In the case of slurry polymerization or bulk polymerization, followed by
gas phase polymerization, even when the initially used catalyst is the
former one, since reaction with an olefin has already been carried out at
the time of the gas phase polymerization, the resulting catalyst is the
same as the latter one to exhibit a superior effectiveness.
The preactivation may be carried out in an inert hydrocarbon solvent such
as propane, butane, n-pentane, n-hexane, n-heptane, benzene, toluene, etc.
and also may be carried out in a liquefied olefin such as liquefied
propylene, liquefied butene-1, etc. or in gaseous ethylene or propylene,
and further, hydrogen gas may be made coexistent in the preactivation
In the preactivation, polymer particles obtained by slurry polymerization,
bulk polymerization or gas phase polymerization may be made coexistent.
Such a polymer may be the same as or different from the olefin polymer as
the object of the polymerization. The quantity of the polymer particles
made coexistent is 0 to 5,000 g per g of the titanium catalyst component.
The solvent or olefin used at the time of the preactivation may be removed
by distilling off under reduced pressure or filtering off midway during
the preactivation or after completion of the preactivation, and further in
order to suspend the solid product in a solvent in a quantity not
exceeding 80 l per g of the product, it is possible to add the solvent to
the product.
The thus obtained catalyst obtained by combining the titanium catalyst
component of the present invention with the organoaluminum compound
(AL.sub.2) and the electron donor (B.sub.4), or the preactivated catalyst
with an olefin, may be used for producing olefin polymers. The
polymerization form in which an olefin is polymerized includes, as
described above, 1 slurry polymerization carried out in a hydrocarbon
solvent such as n-pentane, n-hexane, n-heptane, n-octane, benzene,
toluene, etc., 2 bulk polymerization carried out in a liquefied olefin
monomer such as liquefied propylene, liquefied butene-1, etc., 3 gas phase
polymerization in which an olefin such as ethylene, propylene, etc. is
polymerized in gas phase, and 4 a process wherein two or more of the above
1 to 3 are stepwise combined. Any of the processes are carried out at a
polymerization temperature of room temperature (20.degree. C.) to
200.degree. C., under a polymerization pressure of the atmospheric
pressure (0 Kg/cm.sup.2 G) to 50 Kg/cm.sup.2 G and usually for about 5
minutes to 20 hours.
In the polymerization, addition of a suitable quantity of hydrogen gas for
controlling the molecular weight, etc. are carried out in the same manner
as in conventional polymerization process.
Further, examples of the olefins subjected to polymerization are linear
monoolefins such as ethylene, propylene, butene-1, hexene-1, octene-1,
etc., branched monoolefins such as 4-methylpentene-1, 2-methylpentene-1,
etc., diolefins such as butadiene, isoprene, chloroprene, etc., and these
olefins may be subjected not only to homopolymerization, but to
copolymerization with one another or with another olefin, for example, in
combination of propylene with ethylene, butene-1 with ethylene, propylene
with buene-1, etc. or three components of propylene, ethylene and
butene-1, etc., and further, block copolymerization may be carried out by
varying the kind of the olefin fed at the multi-stage polymerization.
The olefin polymer obtained using the titanium trichloride composition or
the titanium catalyst component of the present invention contains a highly
stereospecific linear olefin-non-linear olefin block copolymer in an
extremely dispersed state; hence when the polymer is made into a film,
voids are few and since the non-linear olefin polymer block of the
specified block copolymer exhibits a nucleating function at the time of
melt-molding, crystallization of the resulting olefin polymer is promoted
so that the transparency and crystallinity of the total olefin polymer are
enhanced.
In particular, in the case where the olefin polymer produced using the
titanium trichloride composition or the titanium catalyst component of the
present invention is a linear olefin polymer such as polypropylene, the
linear olefin polymer block of the linear olefin-nonlinear olefin block
copolymer is compatible with the linear olefin polymer such as
polypropylene so that occurrence of voids in the film prepared from the
olefin polymer is further reduced.
Further, the specified block copolymer introduced into the olefin polymer
by using the titanium trichloride composition or the titanium catalyst
component of the present invention is a stereoregular high molecular
polymer having a high compatibility with the olefin polymer, as described
above, so that the copolymer does not bleed onto the surface of the
resulting olefin polymer.
EXAMPLE
The present invention will be described in more detail by way of Examples,
but it should not be construed to be limited thereto.
The definitions of the terms employed in Examples and Comparative examples
and the measurement methods therein are as follows:
TY: This indicates polymerization activity and refers to a polymer yield
per gram atom of titan (unit: Kg/gram atom).
II: This indicates stereoregularity and refers to a residual quantity after
extraction with n-hexane at 20.degree. C. (unit: % by weight)
BD: Bulk density (unit: g/ml)
MFR: Melt flow rate, JIS K 7210, according to the condition 14 in Table 1
(unit: g/10min.)
Inside haze: This refers to a haze inside a film excluding the surface
influence; an olefin polymer powder is made into a film of 150 .mu. thick
under conditions of a temperature of 200.degree. C. and a pressure of 200
Kg/cm.sup.2 G by means of a press, followed by applying liquid paraffin
onto both the surfaces of the film and measuring the resulting haze
according to JIS K 7105 (unit: .degree.C.).
Crystallization temperature: Measured using a differential scanning
calorimeter at a temperature-lowering rate of 10.degree. C./min. (unit:
.degree.C.).
Flexural elastic modulus:
Tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane
(0.1 part by weight) and calcium stearate (0.1 part by weight) were
blended with an olefin polymer powder (100 parts by weight), followed by
granulating the resulting blend by means of an extrusion-granulator having
a screw bore diameter of 40 mm, molding the resulting granules by means of
an injection-molding machine at a molten resin temperature of 230.degree.
C. and a mold temperature of 50.degree. C. to prepare a JIS type test
piece, allowing this test piece to stand for 72 hours in a room at a
humidity of 50% and at room temperature (23.degree. C.) and measuring the
flexural elastic modulus according to JIS K 7203. (unit: Kgf/cm.sup.2)
Void: An olefin polymer is granulated in the same manner as in the above
item, followed by extruding the resulting granules by means of a T-die
type filmmaking machine at a molten resin temperature of 250.degree. C. to
prepare a sheet of 1 mm thick by means of a cooling roll at 20.degree. C.,
heating the sheet by a hot air at 150.degree. C. for 70 seconds, and
stretching the sheet in both the longitudinal and lateral directions, each
to 7 times the respective original lengths to obtain a biaxially stretched
film of 20 .mu. thick. The film is observed by means of an optical
microscope, followed by measuring the number of voids having a diameter of
10 .mu. or larger. A film having 10 voids or less per cm.sup.2 was denoted
by o; that having 10 to 30 voids per cm.sup.2 was denoted by .DELTA.; and
that having more than 30 voids per cm.sup.2 was denoted by x.
EXAMPLE 1
(1) Preparation of titanium trichloride composition-n-Hexane (6 l),
diethylaluminum monochloride (DEAC) (5.0 mols) and diisoamyl ether (12.0
mols) were mixed at 25.degree. C. for 5 minutes, followed by reacting the
mixture at the same temperature, for 15 minutes to obtain a reaction
solution (I) (the molar ratio of diisoamyl ether/DEAC: 2.4).
TiCl.sub.4 (40 mols) was placed in a nitrogen-purged reactor, followed by
heating it to 35.degree. C., dropwise adding the total quantity of the
above reaction solution (I) over 180 minutes, keeping the mixture at the
same temperature for 60 minutes, raising the temperature up to 80.degree.
C., further reacting the resulting material for one hour, cooling down to
room temperature, removing the supernatant, and 4 times repeating a
procedure of adding n-hexane (20 l) and removing the supernatant by
decantation to obtain a solid product (II).
The total quantity of this product (II) was suspended in n-hexane (30 l),
followed by adding diethylaluminum monochloride (400 g), adding propylene
(1.5 Kg) at 30.degree. C., subjecting the mixture to polymerization
treatment at the same temperature for one hour, thereafter removing the
supernatant by decantation, twice washing the resulting solids with
n-hexane (30 l), successively adding n-hexane (30 l) and diethylaluminum
monochloride (400 g), making the temperature 40.degree. C., adding
vinylcyclohexane (1.9 Kg), subjecting the mixture to polymerization
treatment at 40.degree. C. for 2 hours, thereafter removing the
supernatant, and 5 times repeating a procedure of adding n-hexane (30 l)
and removing the supernatant by decantation to obtain a solid product
(II-A) subjected to a multi-stage polymerization treatment with
propylene-vinylcyclohexane.
The total quantity of this solid product was suspended in n-hexane (9 l),
followed by adding TiCl.sub.4 (3.5 Kg) to the resulting suspension at room
temperature over about 10 minutes, reacting the mixture at 80.degree. C.
for 30 minutes, further adding diisoamyl ether (1.6 Kg), reacting the
mixture at 80.degree. C. for one hour, thereafter 5 times repeating a
procedure of removing the supernatant, and drying under reduced pressure
to obtain a solid product (III) as the titanium trichloride composition of
the present invention.
The content of the propylene polymer block in this titanium crichloride
composition was 25.0% by weight, the content of the vinylcyclohexane
polymer block therein was 25.0% by weight and the titanium content therein
was 12.6% by weight.
(2) Preparation of preactivated catalyst
Into a 80 l capacity stainless reactor provided with slant blades and
purged with nitrogen gas were added n-hexane (40 l), diethylaluminum
monochloride (28.5 g) and the titanium trichloride composition of the
present invention (450 g) obtained above in item (1) at room temperature,
followed by feeding ethylene (0.5 Nm.sup.3) at 30.degree. C. over 2 hours,
reacting the mixture (ethylene reacted per g of the titanium trichloride
composition: 1.0 g), removing unreacted ethylene, washing with n-hexane
and drying to obtain a preactivated catalyst component.
(3) Production of olefin polymer
A polypropylene powder having an MFR of 2.0 (30 Kg) was fed into a 150 l
capacity stainless polymerization vessel of L/D=4 provided with a stirrer
and purged with nitrogen gas, followed by adding n-hexane to the
preactivated catalyst component obtained above in item (2) to prepare a
n-hexane suspension of the component in a concentration of 4.0% by weight,
and continuously feeding the suspension at a rate of 5.1 mg atom/hr as
calculated from titanium atom and a 30% by weight solution of
diethylaluminum monochloride in hexane at a rate of 4.2 g/hr in terms of
diethylaluminum dichloride.
Further, feeding hydrogen gas so as to keep its concentration in the gas
phase of the polymerization vessel at 1.0% by volume and feeding propylene
so as to keep the total pressure at 23 Kg/cm.sup.2 G, the gas phase
polymerization of propylene was continuously carried out at 70.degree. C.
for 160 hours. During the polymerization, the polymer was continuously
withdrawn at a rate of 13.5 Kg/hr so as to give a level of the polymer
retained in the polymerization vessel of 45% by volume. The withdrawn
polymer was successively subjected to contact treatment with nitrogen gas
containing 0.2% by volume of propylene oxide at 95.degree. C. for 30
minutes to obtain polypropylene.
COMPARATIVE EXAMPLE 1
(1) The item (1) of Example 1 was repeated except that the solid product
(II) was converted into a substance corresponding to the solid product
(II-A) without subjecting the product (II) to the multi-stage
polymerization treatment with propylene and vinylcyclohexane, to obtain a
titanium trichloride composition.
(2) The item (2) of Example 1 was repeated except that the titanium
trichloride composition obtained above in the item (1) was used as a
titanium trichloride composition, to prepare a preactivated catalyst
component.
(3) The item (3) of Example 1 was carried out except that the preactivated
catalyst component obtained above in the item (2) was used as a
preactivated catalyst component, to carry out propylene polymerization.
COMPARATIVE EXAMPLE 2
(1) A titanium trichloride composition was obtained in the same manner as
in the item (1) of Comparative example 1.
(2) Into the reactor used in the item (2) of Example 1 were added n-hexane
(20 1), diethylaluminum monochloride (30 g) and the titanium trichloride
composition (180 g) obtained above in the item (1) at room temperature,
followed by adding vinylcyclohexane (150 g), reacting the mixture at
40.degree. C. for 2 hours (the quantity of vinylcyclohexane reacted per g
of the titanium trichloride composition: 0.5 g), thereafter removing the
supernatant by decantation, twice washing the resulting solids with
n-hexane (20 l), successively adding n-hexane (20 l) and diethylaluminum
monochloride (30 g), making the temperature 30.degree. C., adding
propylene (120 g), reacting the mixture at 30.degree. C. for one hour,
successively removing the supernatant, washing with n-hexane, filtering
and drying to obtain a preactivated catalyst component.
(3) The item (3) of Example 1 was repeated except that the catalyst
component obtained above in the item (2) was used as a preactivated
catalyst component, to carry out propylene polymerization. As a result,
since the resulting bulk polymer clogged the withdrawing piping, propylene
polymerization had to be stopped 6 hours after the polymerization
initiation.
COMPARATIVE EXAMPLE 3
(1) The item (1) of Comparative example 1 was repeated except that when the
reaction solution (I) was reacted with TiCl.sub.4, vinylcyclohexane (1.3
Kg) added into n-hexane (100 l was polymerized at 60.degree. C. for 2
hours, separately using a titanium trichloride composition (500 g)
obtained in the same manner as in the item (1) of Comparative example 1
and diethylaluminum monochloride (120 g) as catalyst, followed by washing
with methanol and drying to obtain a vinylcyclohexane polymer (950 g),
grinding this polymer in a 10 l capacity vibration mill at room
temperature for 5 hours and suspending the ground polymer in the
above-mentioned TiCl.sub.4, to obtain a titanium trichloride composition
containing 33.3% by weight of the vinylcyclohexane polymer.
(2) The item (2) of Example 1 was repeated except that the titanium
trichloride composition obtained above in the item (1) was used in place
of the titanium trichloride composition of Example 1, item (2).
(3) The item (3) of Example 1 was repeated except that propylene
polymerization was carried out using the preactivated catalyst component
obtained above in the item (2) in place of the preactivated catalyst
component in Example (1), to obtain a polypropylene.
COMPARATIVE EXAMPLE 4 AND EXAMPLES 2 AND 3
The quantities of propylene and vinylcyclohexane used for the
polymerization treatment in Example 1, item (1) were varied to obtain
titanium trichloride compositions having the respective contents of the
above materials shown in Table listed later. Thereafter, polypropylenes
were obtained in the same manner as in the items (2) and (3) of Example 1.
EXAMPLE 4
n-Heptane (4 l), diethylaluminum monochloride (5.0 mols), diisoamyl ether
(9.0 mols) and di-n-butyl ether (5.0 mols) were reacted at 18.degree. C.
for 30 minutes, followed by dropwise adding the resulting reaction
solution into TiCl.sub.4 (27.5 mols) at 40.degree. C. over 300 minutes,
reacting the mixture at the same temperature for 1.5 hour, raising the
temperature up to 65.degree. C., further reacting for one hour, removing
the supernatant, 6 times repeating a procedure of adding n-hexane (20 l)
and removing the supernatant by decantation, suspending the resulting
solid product (II) (1.8 Kg) in n-hexane (40 l), adding diethylaluminum
monochloride (500 g), and adding and reacting propylene (0.6 Kg) at
30.degree. C. for one hour, to carry out the first step polymerization
treatment.
After lapse of the reaction time, the supernatnat was removed, followed by
twice repeating a procedure of adding n-hexane (20 l) and removing the
supernatant by decantation, successively adding n-hexane (40 l) and
diethylaluminum monochloride (500 g), adding allyltrimethylsilane (3.0
Kg), and reacting the mixture at 50.degree. C. for one hour to carry out
the second step polymerization treatment and thereby obtain a solid
product (II-A) subjected to a multi-stage polymerization treatment with
propylene-allyltrimethylsilane.
After the reaction, the supernatant was removed, followed by twice
repeating a procedure of adding n-hexane (20 l) and removing the
supernatant by decantation, suspending the solid product (II-A) subjected
to the above polymerization treatment in n-hexane (7 l), adding TiCl.sub.4
(1.8 Kg) and n-butyl ether (1.8 Kg), reacting the mixture at 60.degree. C.
for 3 hours, thereafter removing the supernatant by decantation, three
times repeating a procedure of adding n-hexane (20 l), agitating the
mixture for 5 minutes, allowing it to stand still and removing the
supernatant, drying under reduced pressure to obtain a solid product
(III), and polymerizing propylene in the same manner as in the items (2)
and (3) of Example 1 except that the above solid product (III) was used as
a final titanium trichloride composition.
COMPARATIVE EXAMPLE 5
Example 4 was repeated except that the solid product (II) was converted
into a substance corresponding to the solid product (II-A), without the
polymerization treatment with propylene and allyltrimethylsilane, to
obtain a titanium trichloride composition, and propylene was polymerized
using the composition.
EXAMPLE 5
The item (1) of Example 1 was repeated except that diethylaluminum
monochloride (5.0 mols) was replaced by di-n-butylaluminum monochloride
(4.0 mols) to obtain a reaction solution (I), this solution was dropwise
added to TiCl.sub.4 at 45.degree. C. and vinylcyclohexane was replaced by
4,4-dimethylpentene-1 (3.0 Kg), to obtain a titanium trichloride
composition. Thereafter, propylene was polymerized in the same manner as
in the items (2) and (3) of Example 1, to obtain a polypropylene.
COMPARATIVE EXAMPLE 6
Example 5 was repeated except that a multi-stage polymerization treatment
with propylene and 4,4-dimethylpentene-1 was not carried out, to obtain a
titanium trichloride composition. A polypropylene was then obtained.
EXAMPLE 6
The item (1) of Example 1 was repeated except that a multi-stage
polymerization treatment was carried out using 0.9 Kg of propylene and
using 3-methylbutene-1 (1.1 Kg) in place of vinylcyclohexane, and further,
a mixed solution of SiCl.sub.4 (1.8 Kg) with TiCl.sub.4 (2.0 Kg) in place
of TiCl.sub.4 and 2.2 Kg of diisoamyl ether were reacted with the solid
product (II-A), to obtain a solid product (III), and this solid product
(III) was used as a final titanium trichloride composition. Thereafter,
the items (2) and (3) of Example 1 were repeated to obtain a
polypropylene.
COMPARATIVE EXAMPLE 7
Example 6 was repeated except that a titanium trichloride composition was
obtained without carrying out the multi-stage polymerization treatment
with propylene and 3-methylbutene-1, to obtain a polypropylene.
EXAMPLE 7
TiCl.sub.4 (27.0 mols) was added to n-hexane (12 l), followed by cooling
the mixture down to 1.degree. C., further dropwise adding n-hexane (12.5
l) containing diethylaluminum monochloride (27.0 mols) at 1.degree. C.
over 4 hours, thereafter reacting the resulting material at the same
temperature for 15 minutes, successively raising the temperature up to
65.degree. C. over one hour, and reacting at the same temperature for one
hour.
The supernatant was removed, followed by 5 times repeating a procedure of
adding n-hexane (10 l) and removing the supernatant by decantation,
suspending a portion (1.8 Kg) of the resulting solid product (II) (5.7 Kg)
in n-hexane (50 l), adding diethylaluminum monochloride (350 g), further
adding propylene (0.6 Kg) at 30.degree. C., thereafter subjecting it to
polymerization treatment at the same temperature for one hour,
successively removing the supernatant by decantation, washing the
resulting solids with n-hexane (50 l), adding n-hexane (50 l) and
diethylaluminum monochloride (350 g), further adding
p-trimethylsilylstyrene (6.9 Kg) and subjecting the mixture to
polymerization treatment at 40.degree. C. for 2 hours.
After the polymerization treatment, the supernatant was removed, followed
by twice repeating a procedure of adding n-hexane (30 l) and removing the
supernatant by decantation, suspending the total quantity of the resulting
solid product (II-A) subjected to the multistage polymerization treatment
in n-hexane (11 l), adding diisoamyl ether (1.6 l), agitating the
resulting suspension at 35.degree. C. for one hour, 5 times washing with
n-hexane (3 l) to obtain treated solids and suspending the solids in a
n-hexane solution (6 l) containing 40% by volume of TiCl.sub.4.
This suspension was raised to 65.degree. C., followed by reacting it at the
same temperature for 2 hours, thereafter three times washing the resulting
solids with n-hexane (each time 20 l) and drying under reduced pressure to
obtain a solid product (III) as a final titanium trichloride composition.
Successively, in a 200 l capacity polymerization vessel provided with a
stirrer having a two-stage turbine element, n-hexane was added to the
above titanium trichloride composition to prepare a 4.0% by weight
n-hexane suspension, and continuously feeding the suspension at a rate of
12.8 mg atom/hr as calculated from titanium atom and diethylaluminum
monochloride at a rate of 6.2 g/hr, each through the same piping and
n-hexane at a rate of 21 Kg/hr through a separate piping.
Further, feeding hydrogen so as to keep its concentration in the gas phase
of the polymerization vessel at 1.5% by volume, and feeding propylene so
as to keep the total pressure at 10 Kg/cm.sup.2 G, slurry polymerization
of propylene was continuously carried out at 70.degree. C. for 120 hours.
During the polymerization, the resulting slurry was continuously withdrawn
from the polymerization vessel into a 50 l capacity flash tank so as to
give a level of the slurry retained in the polymerization vessel of 75% by
volume. The pressure of the slurry was dropped in the flash tank and
unreacted propylene was removed, while methanol was fed at a rate of 1
Kg/hr and the slurry was subjected to contact treatment at 70.degree. C.
Successively, the solvent was separated from the slurry by means of a
centrifugal separator and the resulting material was dried to obtain a
product powder at a rate of 10 Kg/hr.
COMPARATIVE EXAMPLE 8
Example 7 was repeated except that the solid product (II) was converted
into a substance corresponding to the solid product (II-A) without
carrying out the multistage polymerization treatment with propylene and
p-trimethylsilylstyrene to obtain a titanium trichloride composition.
Slurry polymerization of propylene was carried out using the composition
in the same manner as in Example 7.
EXAMPLE 8
In the item (1) of Example 1, using propylene in a quantity of 0.9 Kg, and
using 2-methyl-4-fluorostyrene (7.6 Kg) in place of vinylcyclohexane, a
multi-stage polymerization was carried out to obtain a solid product
(II-A) subjected to polymerization treatment, followed by adding
TiCl.sub.4 (3.0 Kg) into n-heptane (10 l), adding the total quantity of
the above solid product (II-A) and reacting the mixture at 80.degree. C.
for 30 minutes.
After completion of the reaction, di-n-pentyl ether (2.8 Kg) was further
added, followed by reacting the mixture at 80.degree. C. for one hour to
obtain a solid product (III). Gas phase polymerization of propylene was
carried out in the same manner as in the items (2) and (3) of Example 1
except that the above solid product (III) was used as a final titanium
trichloride composition.
COMPARATIVE EXAMPLE 9
Propylene was polymerized in the same manner as in Example 8 except that a
titanium trichloride composition was obtained without carrying out the
multi-stage polymerization treatment with propylene and
2-methyl-4-fluorostyrene.
EXAMPLE 9
(1) The item (1) of Example 1 was repeated except that the total quantity
of the solid product (II) was suspended in n-hexane (30 l), followed by
adding diethylaluminum monochloride (400 g), feeding ethylene (950 Nl) at
30.degree. C. over one hour to carry out a first step polymerization,
removing unreacted ethylene, adding vinylcyclohexane (1.9 Kg) without
washing the reaction mixture and carrying out a second polymerization
treatment at 40.degree. C. for 2 hours, to obtain a solid product (III) as
the titanium trichloride composition of the present invention.
(2) The item (2) of Example 1 was repeated except that the titanium
trichloride composition obtained above in the item (1) was used as a
titanium trichloride composition, to obtain a preactivated catalyst
component.
(3) Propylene-ethylene copolymerization was carried out in the same manner
as in the item (3) of Example 1 except that the preactivated catalyst
component obtained above in the item (2) was used as a preactivated
catalyst component and ethylene was further fed at the time of the gas
phase polymerization of propylene, so as to keep its concentration in the
gas phase in the polymerization vessel at 0.2% by volume, to obtain a
propylene-ethylene copolymer.
COMPARATIVE EXAMPLE 10
A propylene-ethylene copolymerization was carried out in the same manner as
in the item (1) of Example 9 except that a titanium trichloride
composition was obtained without carrying out the multi-stage
polymerization treatment with ethylene and vinylcyclohexane and the
resulting titanium trichloride composition was used, to obtain a
propylene-ethylene copolymer.
The titanium trichloride compositions obtained in the above Examples and
Comparative examples, polymerization results therewith and evaluation
results thereof are shown in the following Table:
TABLE 1
__________________________________________________________________________
Nos. of
Titanium trichloride composition
Examples
Linear olefin Polymerization results
Evaluation results
and polymer block
Non-linear olefin
TY In-
Crystal-
Flexural
Compar-
Name of polymer block
(Kg/ MFR side
lization
elastic
ative
linear
Content
Name of non-
Content
gram
II BD (g/10
haze
temp.
modulus
examples
olefin
(wt. %)
linear olefin
(wt. %)
atom)
(wt. %)
(g/ml)
min)
(%)
(.degree.C.)
(kgf/cm.sup.2)
Void
__________________________________________________________________________
Ex. 1
Propylene
25.0 Vinylcyclo-
25.0 2650
99.8 0.49
1.7 1.4
130.6
15600 .largecircle.
1
hexane
Com.ex.1
-- -- -- -- 1710
99.6 0.49
1.8 11.6
118.4
12700 .largecircle.
0
Com.ex.2
(*1) -- (*1) -- 1200
98.9 0.40
1.4 2.8
125.4
13900 X
Com.ex.3
-- -- (*2) (33.3)
1700
99.6 0.47
1.6 2.9
125.3
13900 X
Com.ex.4
Propylene
0.01
Vinylcyclo-
0.001
1710
99.6 0.48
1.7 11.0
118.5
12800 .largecircle.
.
hexane
Ex. 2
" 49.3 Vinylcyclo-
1.5 2670
99.8 0.49
1.8 3.0
126.3
14400 .largecircle.
hexane
Ex. 3
" 4.8 Vinylcyclo-
47.6 2640
99.8 0.48
1.7 1.4
130.6
15600 .largecircle.
hexane
Ex. 4
Propylene
12.5 Allyltri-
25.0 2390
99.6 0.50
1.6 1.3
130.3
14800 .largecircle.
methylsilane
Com.ex.5
-- -- -- -- 1550
99.5 0.49
1.6 11.8
118.0
12600 .largecircle.
Ex. 5
Propylene
26.3 4,4-Dimethyl-
21.1 2190
98.5 0.48
1.8 1.7
129.9
14700 .largecircle.
pentene-1
Com.ex.6
-- -- -- -- 1500
98.0 0.48
1.7 11.9
118.2
12600 .largecircle.
Ex. 6
Propylene
18.8 3-Methyl-
18.8 2510
98.3 0.47
1.8 1.5
130.0
15000 .largecircle.
butene-1
Com.ex.7
-- -- -- -- 1640
98.0 0.47
1.7 12.6
118.1
12700 .largecircle.
Ex. 7
Propylene
10.0 p-Trimethyl-
40.0 780
99.6 0.49
1.8 2.3
129.4
14400 .largecircle.
silylstyrene
Com.ex.8
-- -- -- -- 670
99.6 0.49
1.8 12.6
118.4
12600 .largecircle.
Ex. 8
Propylene
20.0 2-Methyl-4-flu-
13.3 2020
98.6 0.48
1.5 2.7
127.5
14600 .largecircle.
orostyrene
Com.ex.9
-- -- -- -- 1370
98.5 0.48
1.6 12.8
118.2
12600 .largecircle.
Ex. 9
Ethylene
25.0 Vinylcyclo-
25.0 2700
97.5 0.46
1.9 1.1
128.0
14600 .DELTA.
hexane
Com.ex.
-- -- -- -- 1730
97.2 0.46
1.9 8.8
116.5
11900 .largecircle.
10
__________________________________________________________________________
(*1) Prepared by preactivating the titanium trichloride composition with
vinylcyclohexane, followed by further preactivating with propylene
(quantities of vinylcyclohexane and propylene reacted with 1 g of titaniu
trichloride composition: each 0.5 g)
(*2) When the titanium trichloride composition was produced, a
vinylcyclohexane polymer separately obtained by polymerization was added.
The main effectiveness of the above items (1) to (9) of the present
invention consists in that when the titanium trichloride composition of
the present invention is used in olefin polymerization as a transition
metal compound catalyst component for producing olefin polymers, it is
possible to produce a highly crystalline olefin polymer without causing
any operational problems and with a very high productivity and when made
into a film, to afford a film having few occurrence of voids and also
having a superior clearance.
As apparent from the above-mentioned Examples, when olefin polymers are
produced using the titanium trichloride composition of the present
invention, a long term stabilized production is possible without any
problem in production. Further, films produced using the resulting olefin
polymer have an inside haze of 1.1 to 3.0%, that is, have a very high
transparency, as compared with the inside hazes about 9 to 13% of films
produced from conventional olefin polymers using titanium trichloride
compositions containing no specified block copolymer. The crystallization
temperature also rose by about 8.degree. C. to about 12.degree. C.,
resulting in a notably improved crystallinity. As a result, the flexural
elastic modulus was also improved (see Examples 1 to 9 and Comparative
examples 1, 5 to 10).
Whereas, according to conventional process of introducing the non-linear
olefin polymer in a manner other than that of the present invention, an
operational problem occurs, and further there are problems that when the
resulting olefin polymer is made into film, voids very often occur in the
film and improvements in the transparency of film and the crystallinity of
the polymer are insufficient due to inferior dispersibility of the polymer
(see Comparative examples 2 and 3).
EXAMPLE 10
(1) Preparation of Titanium Catalyst Component
In a stainless reactor provided with a stirrer, decane (3 l), anhydrous
magnesium chloride (480 g), n-butyl o-titanate (1.7 Kg) and
2-ethyl-1-hexanol (1.95 Kg) were mixed, followed by heating and dissolving
the mixture with stirring at 130.degree. C. for one hour to prepare a
uniform solution, making its temperature 70.degree. C., adding diisobutyl
phthalate (180 g) with stirring, after lapse of one hour, dropwise adding
SiCl.sub.4 (5.2 Kg) over 2.5 hours to deposit solids, further heating at
70.degree. C. for one hour, separating the solids from the solution and
washing with hexane to obtain a solid product (I).
The total quantity of the solid product (I) was suspended in hexane (10 l)
containing triethylaluminum (450 g) and diphenyldimethoxysilane (145 g),
kept at 30.degree. C., followed by adding propylene (630 g), subjecting
the mixture to polymerization treatment with stirring at the same
temperature for one hour, thereafter removing the supernatant by
decantation, twice washing the resulting solids with n-hexane (6 l),
successively adding n-hexane (10 l), triethylaluminum (450 g) and
diphenyldimethoxysilane (145 g) with stirring, making the temperature
30.degree. C., adding vinylcyclohexane (730 g), subjecting the mixture to
polymerization treatment at 30.degree. C. for 2 hours, thereafter removing
the supernatant and 4 times repeating a procedure of adding n-hexane (6 l)
and removing the supernatant to obtain a solid product (II-A) subjected to
a multi-stage polymerization treatment with propylene and
vinylcyclohexane.
The total quantity of the solid product (II-A) was mixed with TiCl.sub.4 (5
l) having 1,2-dichloroethane (5 l) dissolved therein, followed by adding
diisobutyl phthalate (180 g), reacting the mixture with stirring at
100.degree. C. for 2 hours, removing the resulting liquid phase portion by
decantation at the same temperature, again adding 1,2-dichloroethane (5 l)
and TiCl.sub.4 (5 l), agitating the mixture at 100.degree. C. for 2 hours,
washing with hexane and drying to obtain a solid product (III) as the
titanium catalyst component of the present invention.
The titanium catalyst component has a particle form close to sphere and the
contents of the propylene polymer block, the vinylcyclohexane polymer
block and titanium were 30.8% by weight, 30.8% by weight and 1.2% by
weight, respectively.
(2) Preparation of Preactivated Catalyst
Into a 30 l capacity stainless reactor provided with slant blades and
purged with nitrogen gas were added n-hexane (20 l), triethylaluminum (1.5
Kg), diphenyldimethoxysilane (480 g) and the catalyst component (260 g) at
room temperature, followed by keeping the reactor at 30.degree. C.,
feeding ethylene (240 Nl) at the same temperature over 2 hours, reacting
the mixture (the quantity of ethylene reacted per g of the titanium
catalyst component: 1.0 g), and removing unreacted ethylene to obtain a
preactivated catalyst.
(3) Production of Olefin Polymer
Into a 80 l capacity, horizontal type polymerization vessel (L/D=3)
provided with a stirrer and purged with nitrogen gas was fed a
polypropylene powder (20 Kg) having an MFR of 2.0, followed by
continuously feeding the above-mentioned preactivated catalyst slurry
(containing triethylaluminum and diphenyldimethoxysilane besides the
titanium catalyst component) at a rate of 0.286 mg atom/hr as calculated
from titanium atom.
Further, hydrogen gas was fed so as to keep its concentration in gas phase
at 0.15% by volume and also propylene was fed so as to keep the total
pressure at 23 Kg/cm.sup.2 G, followed by continuously carrying out gas
phase polymerization of propylene at 70.degree. C. over 120 hours. During
the polymerization period, the resulting polymer was continuously
withdrawn from the polymerization vessel so as to give the level of the
polymer retained in the polymerization vessel at 60% by volume, at a rate
of 10 Kg/hr.
The withdrawn polymer was successively subjected to contact treatment with
nitrogen gas containing 0.2% by volume of propylene oxide at 95.degree. C.
for 15 minutes to obtain a product powder.
COMPARATIVE EXAMPLE 11
(1) Example 10 (1) was repeated except that a substance corresponding to
the solid product (II) was prepared without subjecting the solid product
(I) to the multi-stage polymerization treatment with propylene and
vinylcyclohexane, to obtain a titanium catalyst component.
(2) Example 10 (2) was repeated except that the titanium catalyst component
(100 g) obtained in the above item (1) was used as a titanium catalyst
component, to prepare a preactivated catalyst.
(3) Example 10 (3) was repeated except that the preactivated catalyst
obtained in the above item (2) was used as a preactivated catalyst, to
carry out propylene polymerization.
COMPARATIVE EXAMPLE 12
(1) A titanium catalyst component was obtained in the same manner as in
Comparative example 11 (1).
(2) Into the reactor used in Example 10 (2) were fed n-heptane (20 l), the
titanium catalyst component (100 g) obtained in the above item (1),
diethylaluminum monochloride (400 g) and diphenyldimethoxysilane (120 g),
followed by adding vinylcyclohexane (130 g), reacting the mixture at
40.degree. C. for 2 hours (the quantity of vinylcyclohexane reacted per g
of the titanium catalyst component: 0.8 g), washing the resulting material
with n-heptane and filtering to obtain solids.
Further, to the solids were added n-heptane (20 l), diethylaluminum
monochloride (400 g) and diphenyldimethoxysilane (55 g), followed by
feeding propylene (120 g) and reacting the mixture at 30.degree. C. for
one hour (the quantity of propylene reacted per g of the titanium catalyst
component: 0.8 g).
(3) Example 10 (3) was repeated except that the preactivated catalyst
slurry was replaced by the catalyst slurry obtained above in the item (2)
and further, triethylaluminum was fed at a rate of 1.7 g/hr and
diphenyldimethoxysilane was fed at a rate of 0.3 g/hr, through separate
feeding ports, respectively, to carry out propylene polymerization. As a
result, since the resulting bulk polymer clogged the powder-withdrawing
piping, the production had to be stopped 5 hours after the polymerization
initiation.
COMPARATIVE EXAMPLE 13
(1) Comparative example 11 (1) was repeated except that in advance of
adding diisobutyl phthalate to a uniform solution of anhydrous magnesium
chloride, n-butyl o-titanate, 2-ethyl-1-hexanol and decane,
vinylcyclohexane (3.6 Kg) added into n-hexane (100 l) was polymerized at
60.degree. C. for 2 hours, using as catalyst, a titanium catalyst
component (100 g) separately obtained in the same manner as in Comparative
example 11 (1), triethylaluminum (35 g) and diphenyldimethoxysilane (7.5
g), followed by washing with methanol, drying, grinding a portion (440 g)
of resulting vinylhexane polymer (3 Kg) in vibrating mill for 5 hours and
suspending the resulting material in the above uniform solution, to obtain
a titanium catalyst component.
(2) Example 10 (2) was repeated except that the titanium catalyst component
obtained above in the item (1) was used as a titanium catalyst component,
to obtain a preactivated catalyst.
(3) Example 10 (3) was repeated except that the preactivated catalyst
obtained above in the item (2) was fed as a preactivated catalyst so as to
keep the total pressure at 23 Kg/cm.sup.2 G, to carry out propylene
polymerization.
COMPARATIVE EXAMPLE 14 AND EXAMPLES 11 AND 12
In Example 10 (1), the respective quantities of propylene and
vinylcyclohexane used for the polymerization treatment were varied to
obtain titanium catalyst components having the contents thereof as shown
in Table listed later. Thereafter, polypropylenes were obtained in the
same manner as in Example 10 (2) and (3).
EXAMPLE 13
Anhydrous aluminum trichloride (1.7 Kg) and magnesium hydroxide (0.6 Kg)
were reacted at 250.degree. C. for 3 hours while grinding them by means of
a vibration mill. As a result, reaction occurred along with evolution of
hydrogen chloride gas. After completion of the heating, the reaction
mixture was cooled in nitrogen gas current to obtain magnesium-containing
solids.
In a stainless reactor provided with a stirrer, decane (6 l), the above
magnesium-containing solids (1.0 kg), n-butyl o-titanate (3.4 Kg) and
2-ethyl-1-hexanol (3.9 Kg) were mixed, followed by heating the mixture
with stirring at 130.degree. C. for 2 hours and dissolving it together to
obtain a uniform solution, making the temperature of the solution
70.degree. C., adding ethyl p-toluylate (0.2 Kg), reacting the mixture for
one hour, adding diisobutyl phthalate (0.4 Kg), further reacting the
mixture for one hour, dropwise adding SiCl.sub.4 stirring over 2 hours 30
minutes, depositing solids, further agitating at 70.degree. C. for one
hour, separating the solids from the solution and washing with purified
hexane to obtain a solid product (I).
The total quantity of the solid product (I) was suspended in hexane (10 l)
containing triethylaluminum (450 g) and methyl p-toluylate (75 g), kept at
25.degree. C., followed by adding propylene (250 g), reacting the mixture
with stirring at 25.degree. C. for one hour to carry out the first stage
polymerization treatment, thereafter removing the supernatant and twice
repeating a procedure of adding n-hexane (6 l) and removing the
supernatant by decantation.
Successively, n-hexane (10 l), triethylaluminum (450 g) and methyl
p-toluylate (75 g) were added with stirring, followed by adding
allyltrimethylsilane (1.3 Kg), reacting the mixture at 25.degree. C. for 2
hours to carry out the second stage polymerization treatment, removing the
supernatant and 4 times repeating a procedure of adding n-hexane (6 l) and
removing the supernatant by decantation, to obtain a solid product (II)
subjected to a multi-stage polymerization treatment with propylene and
allyltrimethylsilane.
The total quantity of the solid product (II) together with TiCl.sub.4 (10
l) diluted with 1,2-dichloroethane (10 l) were added to diisobutyl
phthalate (0.4 Kg), followed by reacting the mixture with stirring at
100.degree. C. for 2 hours, removing the resulting liquid phase portion by
decantation at the same temperature, again adding 1,2-dichloroethane (10
l) and TiCl.sub.4 (10 l), reacting the mixture with stirring at
100.degree. C. for 2 hours, filtering while hot to obtain solid portion,
washing with purified hexane and drying to obtain a solid product (III) as
a final titanium catalyst component.
The contents of the propylene polymer block, the allyltrimethylsilane
polymer block and Ti in the titanium catalyst component were 15.0% by
weight, 35.0% by weight and 1.7% by weight, respectively.
Successively, Example 10 (2) was repeated except that
diphenyldimethoxysilane was replaced by phenyltriethoxysilane (500 g) and
also the above solid product (III) was used as a titanium catalyst
component, to obtain a preactivated catalyst. Thereafter, gas phase
polymerization of propylene was carried out in the same manner as in
Example 10 (3).
COMPARATIVE EXAMPLE 15
Example 13 was repeated except that a substance corresponding to the solid
product (II) was prepared without subjecting the solid product (I) to
polymerization treatment with propylene and allyltrimethylsilane, to
obtain a titanium catalyst component, with which propylene was
polymerized.
EXAMPLE 14
In a stainless reactor provided with a stirrer, n-heptane (8 l), anhydrous
magnesium chloride (1.0 Kg) and n-butyl o-titanate (7.4 Kg) were mixed,
followed by raising the temperature up to 90.degree. C. with stirring,
heating the mixture for 2 hours for dissolution to obtain a uniform
solution, cooling the uniform solution down to 40.degree. C., dropwise
adding methylhydrogenpolysiloxane (1,500 ml), depositing solids and
washing with n-heptane to obtain grey-white solids.
The solids (500 g) and n-heptane (7 l) were placed in a stainless reactor
provided with a stirrer, followed by adding diisobutyl phthalate (100 g),
after elapse of one hour at 30.degree. C., dropwise adding a mixed
solution of SiCl.sub.4 (11.3 Kg) with TiCl.sub.4 (500 g) over one hour,
successively reacting the mixture at 30.degree. C. for 30 minutes and
further at 90.degree. C. for one hour, separating the resulting solids
from the solution and washing with n-heptane to obtain a solid product
(I).
The solid product (I) of 2.5 mols calculated in terms of magnesium atom was
suspended in n-heptane (5 l) containing triethylaluminum (200 g) and
diphenyldimethoxysilane (60 g) kept at 30.degree. C., followed by adding
propylene (200 g) and reacting the mixture with stirring at 30.degree. C.
for one hour, to carry out a first stage polymerization treatment.
After lapse of the reaction time, the supernatant was removed, followed by
twice repeating a procedure of adding n-heptane (6 l) and removing the
supernatant by decantation, successively adding n-heptane (5 l),
triethylaluminum (200 g) and diphenyldimethoxysilane (60 g) with stirring,
adding 4,4-dimethylpentene-1 (280 g), reacting the mixture at 30.degree.
C. for 2 hours to carry out a second stage polymerization treatment,
thereafter separating the resulting solids from the solution and washing
with n-heptane to obtain a solid product (II) subjected to a multi-stage
polymerization with propylene and 4,4-dimethylpentene-1.
The total quantity of the solid product (II) was mixed with an n-heptane
solution (12 l) containing TiCl.sub.4 (6 l), followed by adding diheptyl
phthalate (100 g), reacting the mixture at 50.degree. C. for 2 hours,
washing with n-heptane, further adding TiCl.sub.4 (150 ml) and washing at
90.degree. C. to obtain a solid product (III). The contents of the
propylene polymer block, 4,4-dimethylpentene-1 polymer block and titanium
were 25.0% by weight, 25.0% by weight and 1.5% by weight, respectively.
Successively, Example 1 (2) was repeated except that
diphenyldimethoxysilane was replaced by t-butyltriethoxysilane (150 g) and
also the above solid product (III) (200 g) was used as a titanium catalyst
component, to obtain a preactivated catalyst, with which gas phase
polymerization of propylene was carried out in the same manner as in
Example 10 (3).
COMPARATIVE EXAMPLE 16
Example 14 was repeated except that a substance corresponding to the solid
product (II) was prepared without subjecting the solid product (I) with
propylene and 4,4-dimethylpentene-1, to obtain a titanium catalyst
component, with which gas phase polymerization of propylene was carried
out.
EXAMPLE 15
In a stainless reactor provided with a stirrer, n-decane (2.5 l), anhydrous
MgCl.sub.2 (480 g) and 2-ethyl-1-hexanol (1.95 Kg) were heated at
130.degree. C. for 2 hours for dissolution to obtain a uniform solution,
followed by adding phthalic anhydride (111 g) into the solution, and
mixing these with stirring at 130.degree. C. to dissolve phthalic
anhydride in the uniform solution
The thus obtained uniform solution was cooled down to room temperature,
followed by dropwise adding the total quantity into TiCl.sub.4 (10 l) kept
at -20.degree. C., over 1 hr., raising the temperature of the resulting
mixed solution up to 110.degree. C. over 4 hours, reacting the resulting
material with stirring at the same temperature for 2 hours, separating the
resulting solids from the solution and washing with n-hexane to obtain a
solid product((I).
The total quantity of the solid product (I) was suspended in n-decane (10
l) containing triethylaluminum (450 g) and diphenyldimethoxysilane (145
g), kept at 40.degree. C., followed by adding propylene (470 g), reactng
the mixture with stirring at 40.degree. C. for one hour to carry out a
first stage polymerization treatment, thereafter separating the resulting
solids from the solution, washing with n-hexane, successively adding
n-decane (10 l), triethylaluminum (450 g) and diphenyldimethoxysilane (145
g) with stirring, adding 3-methylbutene-1 (350 g), reacting the mixture at
40.degree. C. for 2 hours to carry out a second stage polymerization
treatment, separating the resulting solids from the solution and washing
with n-hexane, to obtain a solid product (II) subjected to a multi-stage
polymerization treatment with propylene and 3-methylbutene-1.
The total quantity of the solid product (II) was mixed with TiCl.sub.4 (10
l), followed by adding diisobutyl phthalate (350 g), reacting the mixture
with stirring at 110.degree. C. for 2 hours, removing the resulting liquid
phase portion by decantation at the same temperature, and again adding
TiCl.sub.4 (1,000 ml) to carry out heating reaction at 110.degree. C. for
2 hours.
After completion of the reaction, the resulting liquid phase portion was
removed by decantation at the same temperature, followed by washing the
resulting solids with n-decane and n-hexane at 80.degree. C. and drying to
obtain a solid product (III) as a final titanium catalyst component. The
contents of the propylene polymer block, the 3-methylbutene-1 polymer
block and titanium were 30.0% by weight, 20.0% by weight and 1.5% by
weight, respectively.
In a 200 l capacity polymerization vessel provided with a stirrer having
two-stage turbine elements, n-hexane was added to the above titanium
catalyst component to prepare a 4.0% by weight n-hexane suspension,
followed by continuously feeding the suspension at a rate of 0.39 mg
atom/hr calculated in terms of titanium atom,, triethylaluminum at a rate
of 8.5 g/hr and diphenyldimethoxysilane at a rate of 3.0 g/hr, each
through the same piping and n-hexane at a rate of 21 Kg/hr through a
separate piping, further feeding hydrogen gas so as to keep its
concentration in gas phase at 0.25% by volume and propylene so as to keep
the total pressure at 8 Kg/cm.sup.2 G to continuously carry out slurry
polymerization of propylene at 70.degree. C. over 120 hours.
During the polymerization period, the resulting slurry was continuously
withdrawn from the polymerization vessel into a 50 l capacity flash tank
so as to give a level of the slurry retained in the polymerization vessel,
of 75% by volume.
The pressure of the slurry was dropped in the flash tank to remove
unreacted propylene, while methanol was fed at a rate of 1 Kg/hr, to
subject them to contact treatment at 70.degree. C., followed by removing
the solvent from the slurry by means of a centrifuge, and drying the
resulting material by a dryer to continuously obtain a product powder at a
rate of 10 Kg/hr.
COMPARATIVE EXAMPLE 17
Example 15 was repeated except that the solid product (I) was made a
substance corresponding to the solid product (II) without subjecting it to
polymerization treatment with propylene and 3-methylbutene-1 to obtain a
titanium catalyst component, with which slurry polymerization of propylene
was carried out in the same manner as in Example 15.
EXAMPLE 16
Example 10 (1) was repeated except that anhydrous MgCl.sub.2 was replaced
by magnesium ethoxide (580 g), the quantity of propylene used was made 85
g and vinylcyclohexane was replaced by p-trimethylsilylstyrene (1.6 Kg) to
obtain a solid product (III), and using the solid product (III) as a final
titanium catalyst component, gas phase polymerization of propylene was
carried out in the same manner as in Example 10 (2) and (3).
COMPARATIVE EXAMPLE 18
Example 16 was repeated except that the solid product (I) was made into a
substance corresponding to the solid product (II) without subjecting it to
polymerization treatment with propylene and p-trimethylsilylstyrene, to
obtain a titanium catalyst component, with which propylene was
polymerized.
EXAMPLE 17
Example 10 (1) was repeated except that n-butyl o-titanate was replaced by
n-butyl polytitanate (pentamer) (1.2 Kg), the quantity of propylene used
was made 240 g and vinylcyclohexane was replaced by
2-methyl-4-fluorostyrene (2.7 Kg), to obtain a titanium catalyst
component. Using the titanium catalyst component, propylene polymerization
was carried out in the same manner as in Example 10 (2) and (3).
COMPARATIVELY EXAMPLE 19
Example 17 was repeated except that the solid product (I) was made into a
substance corresponding to the solid product (II) without subjecting it to
polymerization treatment with propylene and 2-methyl-4fluorostyrene, to
obtain a titanium catalyst component, with which propylene was
polymerized.
EXAMPLE 18
(1) Example 10 (1) was repeated except that ethylene (950 Nl) in place of
propylene was fed over one hour, followed by subjecting the resulting
solid product (I) to a first stage polymerization treatment, removing
unreacted ethylene, adding vinylcyclohexane (730 g) without washing the
resulting reaction mixture and carrying out a second stage polymerization
treatment at 40.degree. C. for 2 hours, to obtain a solid product (III) as
a titanium catalyst component of the present invention.
(2) Example 10 (2) was repeated except that the titanium catalyst component
obtained above in the item (1) was used as a titanium catalyst component,
to obtain a preactivated catalyst component.
(3) Example 10 (3) was repeated except that the preactivated catalyst
component obtained above in the item (2) was used as a preactivated
catalyst component and ethylene was further fed so as to keep its
concentration in the gas phase of the polymerization vessel at 0.2% by
volume at the time of gas phase polymerization of propylene, to carry out
propylene-ethylene copolymerization and thereby obtain a
propylene-ethylene copolymer.
COMPARATIVE EXAMPLE 20
Example 18 was repeated except that a titanium catalyst component was
obtained without carrying out the multi-stage polymerization treatment
with ethylene and vinylcyclohexane, of Example 18 (1), and the titanium
catalyst component was used, to obtain a propylene-ethylene copolymer.
The titanium catalyst component, polymerization results and evaluation
results of the above Examples and Comparative examples are shown in Table
2.
TABLE 2
__________________________________________________________________________
Nos. of
Titanium catalyst component
Examples
Linear olefin Polymerization results
Evaluation results
and polymer block
Non-linear olefin
TY In-
Crystal-
Flexural
Compar-
Name of polymer block
(Kg/ MFR side
lization
elastic
ative
linear
Content
Name of non-
Content
gram
II BD (g/10
haze
temp.
modulus
examples
olefin
(wt. %)
linear olefin
(wt. %)
atom)
(wt. %)
(g/ml)
min)
(%)
(.degree.C.)
(kgf/cm.sup.2)
Void
__________________________________________________________________________
Ex. 10
Propylene
30.8 Vinylcyclo-
30.8 35000
98.5 0.42
1.9 1.5
130.5
14600 .largecircle.
hexane
Com.ex.
-- -- -- -- 33800
98.0 0.40
2.0 11.8
118.4
11800 .largecircle.
11
Com.ex.
(*1) -- (*1) -- 23700
97.0 0.32
1.4 2.9
125.2
12800 X
12
Com.ex.
-- -- (*2) (44.4)
33600
98.0 0.39
1.9 3.0
125.3
12800 X
13
Com.ex.
Propylene
0.01
Vinylcyclo-
0.001
33900
98.0 0.40
2.0 10.2
118.9
11900 .largecircle.
14 hexane
Ex. 11
" 48.8 Vinylcyclo-
2.4 34300
98.3 0.41
1.9 3.1
124.5
13200 .largecircle.
hexane
Ex. 12
" 48.8 Vinylcyclo-
47.6 34800
98.5 0.41
1.8 1.5
130.6
14600 .largecircle.
hexane
Ex. 13
Propylene
15.0 Allyltri-
35.0 32700
98.2 0.41
1.8 1.4
130.3
14100 .largecircle.
methylsilane
Com.ex.
-- -- -- -- 30600
97.8 0.39
1.8 11.8
118.0
11700 .largecircle.
15
Ex. 14
Propylene
25.0 4,4-Dimethyl-
25.0 34100
98.2 0.38
1.9 1.8
129.4
13400 .largecircle.
pentene-1
Com.ex.
-- -- -- -- 33000
97.7 0.37
1.9 11.8
118.3
11500 .largecircle.
16
Ex. 15
Propylene
30.0 3-Methyl-
20.0 25600
98.3 0.46
1.7 1.6
130.0
14000 .largecircle.
butene-1
Com.ex.
-- -- -- -- 25200
98.1 0.45
1.7 11.9
118.2
11700 .largecircle.
17
Ex. 16
Propylene
4.8 p-Trimethyl-
47.6 35200
97.5 0.39
1.9 2.4
128.0
13500 .largecircle.
silylstyrene
Com.ex.
-- -- -- -- 35000
97.4 0.38
1.9 12.0
118.3
11700 .largecircle.
18
Ex. 17
Propylene
17.6 2-Methyl-4-flu-
23.5 33600
98.2 0.41
1.9 2.8
127.5
13500 .largecircle.
orostyrene
Com.ex.
-- -- -- -- 33400
98.1 0.40
2.0 12.2
118.2
11600 .largecircle.
19
Ex. 18
Ethylene
30.8 Vinylcyclo-
30.8 35200
97.5 0.40
1.8 1.2
127.7
13500 .DELTA.
hexane
Com.ex.
-- -- -- -- 34000
97.2 0.38
1.8 8.7
116.5
10800 .largecircle.
20
__________________________________________________________________________
(*1) For preactivating the catalyst, vinylcyclohexane (quantity reacted
per g of Ti catalyst component: 0.8 g) and propylene (quantity reacted pe
g of Ti catalyst component: 0.8 g) were used.
(*2) At the time of producing Ti catalyst component, a vinylcyclohexane
polymer separately obtained by polymerization was added.
The main effectiveness of the above items (10) to (18) of the present
invention consists in that when the titanium catalyst composition of the
present invention is used as a transition metal compound catalyst
component for producing olefin polymers, in olefin polymerization, it is
possible to produce a highly crystalline olefin polymer having few
occurrence of voids and a superior transparency when made into film,
without causing any operational problems and with a high productivity.
As apparent from the above Examples, when olefin polymers are produced
using the titanium catalyst component composition of the present
invention, no problem on production is raised and a long term, stabilized
production is possible.
Further, films produced from the resulting olefin polymer have an inside
haze of 1.2 to 3.1%, that is, a very high transparency, as compared with
about 9 to 12% of films produced using conventional olefin polymers
produced using a titanium catalyst component containing no specified block
polymer.
Further, the crystallization temperature has been raised by about 6.degree.
to 12.degree. C. to notably improve the crystallinity so that the flexural
elastic modulus has also been improved (see Examples 10-18 and Comparative
examples 11 and 15 to 20).
Whereas, according to a conventional process in which a non-linear olefin
polymer is introduced in a manner other than that of the present
invention, such problems are raised that operational problems occur and
when the resulting polymer is made into films, voids very often occur and
improvements in the transparency and crystallinity are also insufficient
due to inferior dispersibility (see Comparative examples 12 and 13).
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